Nickel manganese composite hydroxide particles and manufacturing method thereof, cathode active material for a non-aqueous electrolyte secondary battery and manufacturing method thereof, and a non-aqueous electrolyte secondary battery

ABSTRACT

Provided are nickel manganese composite hydroxide particles that are a precursor for forming cathode active material comprising lithium nickel manganese composite oxide having hollow structure of particles having a small and uniform particle size for obtaining a non-aqueous electrolyte secondary battery having high capacity, high output and good cyclability. 
     When obtaining the nickel manganese composite hydroxide particles from a crystallization reaction, an aqueous solution for nucleation, which includes at least a metallic compound that contains nickel and a metallic compound that contains manganese, and does not include a complex ion formation agent that forms complex ions with nickel, manganese and cobalt, is controlled so that the temperature of the solution is 60° C. or greater, and so that the pH value that is measured at a standard solution temperature of 25° C. is 11.5 to 13.5, and after nucleation is performed, an aqueous solution for particle growth, which includes the nuclei that were formed in the nucleation step and does not substantially include a complex ion formation agent that forms complex ions with nickel, manganese and cobalt, is controlled so that the temperature of the solution is 60° C. or greater, and so that the pH value that is measured at a standard solution temperature of 25° C. is 9.5 to 11.5, and is less than the pH value in the nucleation step.

TECHNICAL FIELD

The present invention relates to nickel manganese composite hydroxideparticles, which are a precursor to cathode active material for anon-aqueous electrolyte secondary battery, and the manufacturing methodthereof, cathode active material for a non-aqueous electrolyte secondarybattery, which uses the nickel manganese composite hydroxide particlesas a raw material, and the manufacturing method thereof, and anon-aqueous electrolyte secondary battery that uses the cathode activematerial for a non-aqueous electrolyte secondary battery as the cathodematerial.

BACKGROUND ART

In recent years, as portable electronic devices such as mobiletelephones and notebook personal computers become widespread, there is alarge need for development of compact and lightweight non-aqueouselectrolyte secondary batteries that have high energy density. Moreover,there is also a strong need for development of a high-output secondarybattery as a motor drive battery, and particularly, as a battery for thepower source of transport equipment.

As a secondary battery that satisfies this kind of need is a lithium-ionrechargeable battery. A lithium-ion rechargeable battery comprises ananode, a cathode and an electrolyte, and a material in which lithium canbe desorbed and inserted is used as the active material for the anodeand cathode.

Currently, much research and development is being performed related tolithium-ion batteries, and of that, research of lithium-ion batteriesthat use layered or spinel type lithium metal composite oxide as thecathode material has been advancing as high-energy density batteriesthat are capable of 4V class high voltage.

Currently, as the cathode material of that kind of lithium-ion secondarybattery, lithium composite oxides such as lithium cobalt composite oxide(LiCoO₂) having a relatively simple composition, lithium nickelcomposite (LiNiO₂), which uses nickel that is less expensive thancobalt, lithium nickel manganese cobalt composite oxide(LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂), lithium manganese composite oxide(LiMn₂O₄) that uses manganese, and lithium nickel manganese compositeoxide (LiNi_(0.5)Mn_(0.5)O₂) have been proposed.

Among these cathode active materials, lithium nickel manganese compositeoxide ((LiNi_(0.5)Mn_(0.5)O₂), which is high capacity, has excellentthermal stability and does not use cobalt of which there are fewreserves, has gained much attention in recent years. Lithium nickelmanganese composite oxide ((LiNi_(0.5)Mn_(0.5)O₂) is layered in the sameway as lithium cobalt composite oxides and lithium nickel compositeoxides, and nickel and manganese are included in transitional metalsites at basically a compositional ratio of 1:1 (Ohzuku et al., “LayeredLithium Insertion Material of LiNi_(1/2)Mn_(1/2)O₂: A PossibleAlternative to LiCoO₂ for Advanced Lithium-Ion Batteries”, ChemistryLetters, Vol. 30 (2001), No. 8, p. 744).

Incidentally, as a condition for a lithium ion secondary battery toobtain good performance characteristics such as high output, lowresistance, high cyclability, and high capacity, cathode materialcomprising particles having a uniform and suitable particle size isrequired.

This is because, when a cathode material having a large particle sizeand low specific surface area is used, the reactive area with theelectrolyte cannot be sufficiently maintained, so the reactionresistance rises, and it is not possible to obtain a battery having highoutput. Moreover, when a cathode material having a wide particle sizedistribution is used, the voltage applied to the particles in theelectrode become uneven, and when the battery is repeatedly recharged,small particles selectively deteriorate, and the capacity decreases.

In aiming for high output of a lithium-ion secondary battery, shorteningthe distance between the cathode and anode is effective, so preferablythe cathode plate is made to be thin, and from this aspect as well,using cathode material having a small particle size is useful.

Therefore, in order to improve the performance of the cathode material,it is important that lithium nickel manganese composite oxide, which isa cathode active material, be manufactured so that the particle size issmall and uniform.

Lithium nickel manganese composite oxide is normally manufactured fromcomposite hydroxide, so in order to make the lithium nickel manganesecomposite oxide particles small with a uniform size, it is necessary touse a composite hydroxide as the raw material that has small particleswith a uniform particle size.

In other words, in order to improve the performance of the cathodematerial and manufacture a high-performance lithium-ion secondarybattery as a final product, it is necessary to use a composite hydroxidethat comprises particles having a small particle size and narrowparticle distribution as the composite hydroxide that will become theraw material of the lithium nickel manganese composite oxide used informing the cathode material.

As a nickel manganese composite hydroxide that is used as the rawmaterial of a lithium nickel manganese composite oxide, proposed aremanganese nickel composite hydroxide particles as disclosed inJP2004-210560(A) which are composite hydroxide particles having amanganese to nickel ratio of 1:1, with an average particle size of 5 to15 μm, tap density of 0.6 to 1.4 g/ml, bulk density of 0.4 to 1.0 g/ml,specific surface area of 20 to 55 m²/g, amount of sulfate radicalcontained being 25 to 45 weight %, and in X-ray diffraction, a ratio(I₀/I₁) of the maximum strength (I₀) of the peak in the range 15≦2θ≦25and the maximum strength (I₁) of the peak in the range 30≦2θ≦40 of 1 to6. The secondary particle surface and internal structure is formed in anetlike structure with fold-like walls of primary particles, with thespace surrounded by the fold-like walls being relatively large.

Furthermore, as the manufacturing method, a method is disclosed inwhich, while keeping the amount of oxidation of manganese ions within aset range, a mixed aqueous solution of manganese salt and nickel salthaving a atomic ratio of manganese and nickel of 1:1 is mixed andreacted with an alkaline solution in an aqueous solution having a pH of9 to 13 with the existence of a complexing agent to causecoprecipitation of particles.

However, in the case of the lithium manganese nickel composite oxide andmanufacturing method disclosed in JP2004-210560(A), when investigatingthe structure of the particles, it can be clearly seen in the disclosedelectron micrograph that coarse particles and fine particles are mixedtogether in the obtained particles, and making the particle size uniformhas not been considered.

On the other hand, in regards to the particle size distribution oflithium composite oxide particles, a lithium composite oxide has beendisclosed in JP2008-147068(A) such that in the particle sizedistribution curve, the particles have a particle size distribution withan average particle size D50, which means the particle size of acumulative frequency of 50%, of 3 to 15 μm, a minimum particle size of0.5 μm or greater, and a maximum particle size of 50 μm or less, andwhere in the relationship between average particle size D10 at acumulative frequency of 10% and D90 at a cumulative frequency of 90%,the ratio D10/D50 is 0.60 to 0.90, and the ratio D10/D90 is 0.30 to0.70. It has also been disclosed that this lithium composite oxide hashigh repletion, excellent discharge capacity characteristic and highoutput characteristic, and does not easily deteriorate even underconditions of a large discharge load, so by using this lithium compositeoxide, a non-aqueous electrolyte lithium ion secondary battery havingexcellent output characteristics and little deterioration of cyclabilitycan be obtained.

However, the lithium composite oxide disclosed in JP2008-147068(A)includes fine particles and coarse particles as a minimum particle size0.5 μm or greater and a maximum particle size of 50 μm or less withrespect to an average particle size of 3 to 15 μm. The particle sizedistribution that is regulated by D10/D50 and D10/D90 is not a narrowparticle size distribution range. In other words, the lithium compositeoxide of JP2008-147068(A) does not have sufficiently high uniformity ofparticle size, and when that lithium composite oxide is used, animprovement in performance of the cathode material cannot be expected,and it is difficult to obtain a non-aqueous electrolyte lithium-ionsecondary battery having sufficient performance.

Moreover, a method for manufacturing a composite hydroxide that willbecome the raw material for a composite oxide aimed at improving theparticle size distribution has been disclosed. In JP2003-86182(A), in amethod for manufacturing a cathode active material for a non-aqueouselectrolyte battery, a method for obtaining a hydroxide or oxide as aprecursor is disclosed in which an aqueous solution containing two ormore kinds of transition metal salts, or an aqueous solution containingtwo or more different transition metal salts and an alkaline solutionare simultaneously put into a reaction vessel, and co-precipitation isperformed while causing the solution to coexisting with a reducing agentor by passing an inert gas though the solution.

However, the technology disclosed in JP2003-86182(A) is for recoverywhile classifying the generated crystals, so in order to obtain amaterial having uniform particle size, strictly managing themanufacturing conditions is considered to be necessary, so production onan industrial scale is difficult. Moreover, even though it is possibleto obtain crystal grain having a large grain size, obtaining smallparticles is difficult.

Furthermore, in order to make a battery with high output, increasing thesize of the reactive area without changing the particle size iseffective. In other words, by making particles that are porous, or thathave a hollow particle structure, it is possible to increase the surfacearea that contributes to the battery reaction, and it is possible toreduce the reaction resistance.

For example, in JP2004-253174(A), cathode active material for anon-aqueous electrolyte secondary battery having at least a layeredstructure of a lithium transition metal composite oxide is disclosedwherein the lithium transition metal composite oxide comprises hollowparticles having a shell section on the outside and a hollow section onthe inside of the outer shell section. Also disclosed is that thiscathode active material for a non-aqueous electrolyte secondary batteryhas excellent battery characteristics such as cycle characteristics,output characteristics, thermal stability and the like, and can suitablybe used for a lithium-ion secondary battery.

However, cathode active materials disclosed in JP2004-253174(A) isexpected to have a greater specific surface area than solid particlesbecause the cathode active material has hollow particles, butJP2004-253174(A) does not mention the particle size thereof. Therefore,improvement in reactivity with the electrolyte due to an increase inspecific surface area can be expected, however, the effect on themigration distance of the lithium ions due to making the particlessmaller is not clear, and a sufficient improvement in outputcharacteristics cannot be expected. Furthermore, in regards to theparticle size distribution, the particle size distribution is consideredto be the same as in conventional cathode active material, so selectivedeterioration of minute particles due to uneven voltage that is appliedinside the electrodes occurs, and there is a strong possibility thatthere will be a drop in battery capacity.

As described above, currently neither a lithium composite oxide that cansufficiently improve the performance of a lithium-ion secondary battery,nor a composite hydroxide that will become the raw material for thatcomposite oxide have been developed. Moreover, after investigatingvarious method for manufacturing composite hydroxides, currently amethod that is capable on an industrial scale to manufacture a compositehydroxide that can become the raw material for a composite oxide capableof improving the performance of a lithium-ion secondary battery has notbeen developed. In other words, a cathode active material havingparticles with a small and uniform particle size, and that have a largereactive area, for example having a hollow structure, having not beendeveloped, and a method capable of industrially manufacturing that kindof cathode active material is desired.

RELATED LITERATURE Patent Literature

-   [Patent Literature 1] JP2004-210560(A)-   [Patent Literature 2] JP2008-147068(A)-   [Patent Literature 3] JP2003-86182(A)-   [Patent Literature 4] JP2004-253174(A)

Non-Patent Literature

-   [Non-patent Literature 1] Ohzuku et al., “Layered Lithium Insertion    Material of LiNi_(1/2)Mn_(1/2)O₂: A Possible Alternative to LiCoO₂    for Advanced Lithium-Ion Batteries”, Chemistry Letters, Vol. 30    (2001), No. 8, p. 744

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

In consideration of the problems above, an object of the presentinvention is to provide nickel manganese composite hydroxide particlesthat, when used as a raw material, a lithium nickel manganese compositeoxide is obtained that has small particles with a uniform particle size,and that due to a hollow particle structure have a high specific surfacearea.

Moreover, another object of the present invention is to provide acathode active material for a non-aqueous electrolyte secondary batterythat can reduce the value of the cathode resistance that is measuredwhen used in a battery, and to provide a non-aqueous electrolytesecondary battery that uses that cathode active material and that hashigh capacity, good cyclability and high output.

Furthermore, another object of the present invention is to provide amethod for industrially manufacturing the nickel manganese compositehydroxide particles and cathode active material.

Means for Solving the Problems

The inventors diligently studied the use of lithium nickel manganesecomposite oxide, which is capable of displaying excellent batterycharacteristics, as the cathode material for a lithium ion secondarybattery, and as a result, obtained was a technical knowledge that bycontrolling the particle size distribution of nickel manganese compositehydroxide, which is the raw material, and by giving nickel manganesecomposite hydroxide a structure provided with a center sectioncomprising fine primary particles and an outer shell section on theoutside of the center section comprising of primary particles that arelarger than the primary particles of the center section, it is possibleto obtain lithium nickel manganese composite oxide having hollowstructure and comprising small particles with a highly uniform particlesize. Also obtained was a technical knowledge that by dividingcrystallization into a nucleation step and a particle growth step bycontrolling the pH and using an aqueous solution in each step that doesnot substantially include a complex ion formation agent that formscomplex ions with nickel, manganese and cobalt, the above nickelmanganese composite hydroxide can be obtained. The present invention wasachieved based on the above technical knowledge obtained by theinventors.

In other words, a manufacturing method of nickel manganese compositehydroxide particles of the present invention is

a method for manufacturing nickel manganese composite hydroxideparticles by a crystallization reaction such that the nickel manganesecomposite hydroxide particles can be expressed by the general formulaNi_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a) (where x+y+z+t=1, 0.3≦x≦0.7,0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, 0≦a≦0.5, and M is one or more addedelement that is selected from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Moand W),

the manufacturing method comprising:

a nucleation step of controlling an aqueous solution for nucleation,which includes at least a metallic compound that contains nickel and ametallic compound that contains manganese, and does not include acomplex ion formation agent that forms complex ions with nickel,manganese and cobalt, so that the temperature of the solution is 60° C.or greater, and so that the pH value that is measured at a standardsolution temperature of 25° C. is 11.5 to 13.5, and generating nuclei ascenter sections comprising fine primary particles; and

a particle growth step of controlling an aqueous solution for particlegrowth, which includes the nuclei that were formed in the nucleationstep and does not substantially include a complex ion formation agentthat forms complex ions with nickel, manganese and cobalt, so that thetemperature of the solution is 60° C. or greater, and so that the pHvalue that is measured at a standard solution temperature of 25° C. is9.5 to 11.5, and is less than the pH value in the nucleation step, andgrowing an outer shell section comprising primary particles having aplate shape or needle shape that is larger than the fine primaryparticles on an outer surface of the nuclei.

In the nucleation step and particle growth step, preferably the oxygenconcentration inside the reaction tank is controlled to be 10% by volumeor less.

The aqueous solution resulting from adjusting the pH value of theaqueous solution for nucleation after the nucleation step has finishedcan be used as the aqueous solution for particle growth. Alternatively,it is possible to use a solution that is obtained by adding an aqueoussolution, which contains the nuclei formed in the nucleation step, to acomponent adjustment aqueous solution, which is separate from theaqueous solution for nucleation in which the nuclei were formed, doesnot substantially include a complex ion formation agent that formscomplex ions with nickel, manganese and cobalt, and is controlled sothat the solution temperature is 60° C. or greater, and so that the pHvalue that is measured at a standard solution temperature of 25° C. is9.5 to 11.5 and is lower than the pH value in the nucleation step, asthe aqueous solution for particle growth.

Preferably, the particle growth step starts after part of the liquidcomponent of the aqueous solution for particle growth has been removed.

Furthermore, in the nucleation step and particle growth step whenmanufacturing nickel manganese composite hydroxide that includes one ormore kinds of added elements, it is possible for the aqueous solutionfor nucleation or the aqueous solution for particle growth to be anaqueous solution that is obtained by adding an aqueous solution in whicha salt containing the one or more added elements is added to a mixedsolution that includes a nickel containing metal compound and amanganese containing metal compound, and that does not substantiallyinclude a complex ion formation agent that forms complex ions withnickel, manganese and cobalt.

Alternatively, the nickel composite hydroxide that was obtained in theparticle growth step can be covered with a compound containing the oneor more added elements. As this covering method, there is a methodwherein the one or more added elements are caused to be deposited ontothe surface of nickel manganese composite hydroxide by adding an aqueoussolution containing the one or more added elements to a solution inwhich nickel manganese composite hydroxide is suspended, whilecontrolling the pH at a specified value; there is a method wherein aslurry, in which nickel manganese composite hydroxide and a saltcontaining the one or more added elements are suspended, is sprayed anddried; or there is a method wherein nickel manganese composite hydroxideand a salt containing the one or more added elements are mixed in asolid phase method. Particularly, when a complex ion formation agentother than a complex ion formation agent that forms complex ions withnickel, manganese and cobalt forms complex ions between it and a pHadjustment agent for controlling the pH value of each reaction solution,covering with the added elements is necessary.

The nickel manganese composite hydroxide particles of the presentinvention are nickel manganese composite hydroxide particles that areexpressed by the general formula Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a)(where x+y+z+t=1, 0.3≦x≦0.7, 0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, 0≦a≦0.5, andM is one or more added element that is selected from among Mg, Ca, Al,Ti, V, Cr, Zr, Nb, Mo and W), and that are spherical shaped secondaryparticles that are formed by a plurality of aggregate primary particles,wherein the secondary particles have an average particle size of 3 to 7μm, a value [(d90−d10)/average particle size], which is an indexindicating the extent of the particle size distribution, of 0.55 orless, the particles having a center section comprising fine primaryparticles, and an outer shell section on the outside of the centersection comprising plate shaped or needle shaped primary particles thatare larger than the fine primary particles, with the thickness of theouter shell section being 0.3 to 3 μm.

Preferably, the fine primary particles have an average particle size of0.01 to 0.3 μm, and the plate shaped or needle shaped primary particlesthat are larger than the fine primary particles have an average particlesize of 0.3 to 3 μm, and preferably, the ratio of the thickness of theouter shell section with respect to the particle size of the secondaryparticles is 10 to 45%.

Moreover, preferably, the one or more added elements are uniformlydistributed inside the secondary particles and/or uniformly cover thesurface of the secondary particles.

Also, preferably, the nickel manganese composite hydroxide particles ofthe present invention are generated by the manufacturing method forcomposite hydroxide particles of the present invention.

The manufacturing method for manufacturing cathode active material ofthe present invention is

a manufacturing method for manufacturing cathode active material for anon-aqueous electrolyte secondary battery comprising lithium nickelmanganese composite oxide having layered hexagonal crystal structure andexpressed by the general formula: Li_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂(where −0.05≦u≦0.50, x+y+z+t=1, 0.3≦x≦0.7, 0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1,M is an added element selected from one or more elements from among Mg,Ca, Al, Ti, V, Cr, Zr, Nb, Mo and W),

the manufacturing method comprising:

a mixing step that mixes a lithium compound into the nickel manganesecomposite hydroxide particles of any one of the claims 7 to 11 to form alithium mixture; and

a calcination step that performs calcination of the mixture formed inthe mixing step in an oxygen atmosphere at a temperature of 800 to 980°C.

Preferably, the lithium mixture is adjusted so that the ratio of the sumof the number of metal atoms other than lithium included in the lithiummixture and the number of lithium atoms is 1:0.95 to 1.5.

Moreover, preferably, in the calcination step, temporary calcination hasalready been performed before calcination at a temperature of 350 to800° C.

Furthermore, preferably, the oxygen atmosphere during the calcinationstep is an atmosphere having an oxygen content of 18 to 100% by volume.

The cathode active material of the present invention is expressed by thegeneral formula: Li_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂ (where −0.05≦u≦0.50,x+y+z+t=1, 0.3≦x≦0.7, 0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, M is an addedelement selected from one or more elements from among Mg, Ca, Al, Ti, V,Cr, Zr, Nb, Mo and W), and comprises lithium nickel manganese compositeoxide that is formed from a layered hexagonal crystalline lithiumcontaining composite oxide having an average particle size of 2 to 8 μm,a value [(d90−d10)/average particle size], which is an index indicatingthe extent of the particle size distribution, of 0.60 or less, aspecific surface area of 1 to 2 m²/g, and having a hollow structurecomprising a hollow section inside the particles and an outer shellsection on the outside, with the thickness of the outer shell sectionbeing 0.5 to 2.5 μm.

Preferably, the ratio of the thickness of the outer shell section withrespect to the particle size of the lithium nickel manganese compositeoxide particles is 5 to 45%.

Moreover, preferably, the cathode active material for a non-aqueouselectrolyte secondary battery of the present invention is generated bythe manufacturing method for cathode active material of the presentinvention.

In a non-aqueous electrolyte secondary battery of the present invention,the cathode is formed using the cathode active material for anon-aqueous electrolyte secondary battery above.

Effect of the Invention

With the present invention it is possible to industrially providecathode active material for a non-aqueous electrolyte secondary batterycomprising lithium nickel manganese composite oxide having a small anduniform particle size and having high specific surface area by havinghollow structure. By using this cathode active material as the cathodematerial, the high capacity, high output and cyclability of the batteryare also good.

The manufacturing methods for manufacturing the cathode active materialof the present invention and the nickel manganese composite hydroxideparticles as a precursor can both be easily applied to large-scaleproduction, so can be said to have a large industrial value.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flowchart of a process for manufacturing the nickelmanganese composite hydroxide of the present invention.

FIG. 2 is a flowchart of another process for manufacturing the nickelmanganese composite hydroxide of the present invention.

FIG. 3 is a flowchart of a process for manufacturing a lithium nickelmanganese composite oxide, which is a cathode active material, from thenickel manganese composite hydroxide of the present invention.

FIG. 4 is a flowchart of the flow from manufacturing the nickelmanganese composite hydroxide to manufacturing a non-aqueous electrolytesecondary battery.

FIG. 5 is an SEM photograph of the nickel manganese composite hydroxideof the present invention (1,000× magnification rate).

FIG. 6 is an SEM photograph of a cross section of the nickel manganesecomposite hydroxide of the present invention (10,000× magnificationrate).

FIG. 7 is an SEM photograph of the lithium nickel manganese compositeoxide, which is a cathode active material, of the present invention(1,000× magnification rate).

FIG. 8 is an SEM photograph of a cross section of the lithium nickelmanganese composite oxide, which is a cathode active material, of thepresent invention (10,000× magnification rate).

FIG. 9 is a cross-sectional view of a coin-type battery that was usedfor battery evaluation.

FIG. 10 is a drawing for explaining the evaluation circuit that was usedfor measurement and analysis in impedance evaluation.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to (1) nickel manganese compositehydroxide particles, which are the precursor for a cathode activematerial for a non-aqueous electrolyte secondary battery and themanufacturing method thereof, (2) a cathode active material for anon-aqueous electrolyte secondary battery that uses the nickel manganesecomposite hydroxide and the manufacturing method thereof, and (3) anon-aqueous electrolyte secondary battery that uses the cathode activematerial for a non-aqueous electrolyte secondary battery for thecathode.

In order to improve the performance of a non-aqueous electrolytesecondary battery, the effect of a cathode active material for anon-aqueous electrolyte secondary battery that is used for the cathodeis large. In order to obtain a cathode active material for a non-aqueouselectrolyte secondary battery that can obtain excellent batteryperformance, the particle size, particle size distribution and thespecific surface area are important factors, and a cathode activematerial having a desired particle structure, and that has been adjustedto have a desired particle size and particle size distribution ispreferred. In order to obtain that kind of cathode active material, itis necessary to use a nickel manganese composite hydroxide as rawmaterial that has a desired particle structure as well as a desiredparticle size and particle size distribution.

The invention according to (1) to (3) above is described in detailbelow, however, first, the nickel manganese composite hydroxideparticles and manufacturing method thereof, which are the main featuresof the present invention, will be explained.

(1-1) Nickel Manganese Composite Hydroxide Particles

The nickel manganese composite hydroxide particles of the presentinvention are expressed by the general expression:Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a) (where x+y+z+t=1, 0.3≦x≦0.7,0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, 0≦a≦0.5, and M is one or more additionalelement that is selected from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Moand W), the secondary particles have an average particle size of 3 to 7μm, the index for indicating the spread of the particle sizedistribution [(d90−d10)/average particle size] is 0.55 or less, there isa center section comprising fine primary particles, and an outer shellsection having a thickness of 0.3 to 3 μm on the outside of the centersection that comprises primary particles having a plate shape or needleshape that is larger than the fine primary particles.

The composite hydroxide particles above are particularly suited as theraw material for the cathode active material having a hollow structureof the present invention, so in the following explanation it is presumedthat these composite hydroxide particles are used as the raw materialfor the cathode active material of the present invention.

(Particle Structure)

As illustrated in the example in FIG. 5, the composite hydroxideparticles of the present invention are spherical particles. Morespecifically, as illustrated in the example in FIG. 6, a plurality ofprimary particles are aggregated together to form spherical secondaryparticles, even more specifically, the particles comprise a structurewherein the interior of the particles have a center section comprisingfine primary particles, and shell section on the outside of the centersection comprising a plate shaped or needle shaped primary particlesthat are larger than the fine primary particles. With this structure, inthe sintering process for forming the lithium nickel manganese compositeoxide, which is the cathode active material of the present invention,dispersion of lithium inside the particles is performed sufficiently, soit is possible to obtain a good cathode active material having a uniformdistribution of lithium.

Here, the center section is a structure comprising a collection of fineprimary particles, so when compared with the outer shell section thatcomprises larger thick plate shaped primary particles, in the sinteringprocess above, sintering and a contraction reaction start from a lowertemperature. After that, sintering and the contraction reaction proceedtoward the outer shell where progress is slow, so space occurs in thecenter section. The reaction activity of the fine crystal of the centersection is very high, the contraction rate is also very high, and thefine crystals are absorbed by the large primary particles of the outershell due to Ostwald growth, so a sufficiently large space is formedinside the center section. As a result, the cathode active material thatis obtained after calcination has a hollow structure.

Moreover, it is more preferable that the outer shell of secondaryparticles be formed with the plate shaped or needle shaped primaryparticles being aggregated in random directions. By the plate shaped orneedle shaped primary particles being aggregated in random directions,nearly uniform spacing occurs between the primary particles, and whenmixing and calcining the lithium compound, the molten lithium compoundmoves inside the secondary particles, and dispersion of the lithium isadequately performed. Furthermore, by aggregating those particles inrandom directions, absorption of the particles of the center sectionduring the calcination process occurs evenly, so it is possible to formspaces of suitable size inside the cathode active material, and so ispreferred from this aspect as well.

In order to form space during the calcination process, preferably theaverage particle size of the fine primary particles is 0.01 to 0.3 μm,and more preferably is 0.1 to 0.3 μm. Moreover, preferably the averageparticle size of the plate shaped or needle shaped primary particles,which are larger than the fine primary particles, is 0.3 to 3 μm, andmore preferably is 0.4 to 1.5 μm, and particularly, even more preferablyis 0.4 to 1.0 μm. When the average particle size of the fine primaryparticles is less than 0.01 μm, a center section having a sufficientsize may not be formed in the composite hydroxide particles, and whenthe average particle size is greater then 0.3 μm, absorption of thecenter section is not sufficient, so it is possible that a space ofadequate size will not be obtained after calcination. On the other hand,when the average particle size of the plate shaped or needle shapedparticles of the outer shell section is less than 0.3 μm, sintering isperformed at low temperature during calcination, and it may not bepossible to obtain space having an sufficient size, and when greaterthan 3 μm, in order for the crystallinity of the obtained cathode activematerial to be suitable, it is necessary to increase the calcinationtemperature, so sintering will occur between the secondary particles andthe particle size of the obtained cathode active material will exceedthe range above.

Furthermore, preferably the fine primary particles are plate shaped orneedle shaped. By the fine primary particles having these shapes, thedensity of the center section is sufficiently low, large contractionoccurs due to calcination, and a sufficient amount of space is created.

For the secondary particles, it is necessary that the thickness of theouter shell section be 0.3 to 3 μm. When the thickness of the outershell section is less than 0.3 μm, contraction of the outer shell duringcalcination is larger, and sintering of the surrounding secondaryparticles also proceeds, so the form of the secondary particles cannotbe maintained. When the thickness exceeds 3 μm the structure of theouter shell becomes dense, so there is a problem in that holes passingthrough to the center section are not formed, and the center sectioncannot be used as a reaction surface. From the aspect of stableproductivity, the thickness is preferably 0.5 to 1.5 μm.

Moreover, in the case of the secondary particles above, preferably thethickness of the outer shell section is 10 to 45% the particle size ofthe secondary particles, and more preferably 10 to 40%, and even morepreferably 10 to 35%. The cathode active material that is obtained withthe composite hydroxide above as the raw material has hollow structure,and the ratio of the thickness of the outer shell section with respectto the particle size is maintained at that ratio for the compositehydroxide secondary particles above. Therefore, by keeping the ratio ofthe thickness of the outer shell section with respect to the size of thesecondary particles within the range above, it is possible to form asufficient hollow section in the lithium nickel manganese compositeoxide particles. When the thickness of the outer shell section is sothin that the ratio with respect to the particle size of the secondaryparticles is less than 10%, the contraction of the composite hydroxideparticles in the calcination process when manufacturing the cathodeactive material becomes large, and sintering occurs between thesecondary particles of the lithium nickel manganese composite oxide, sothere is a possibility that the particle size distribution of thecathode active material becomes poor. On the other hand, when the ratioexceeds 45%, problems such as not being able to form a sufficientlylarge center section may occur.

The particle size of the fine primary particles and the plate shaped orneedle shaped primary particles, the thickness of the outer shellsection of secondary particles, and the ratio of the thickness of theouter shell section with respect to the particle size of the secondaryparticles can be measured by using a scanning electron microscope toobserve the cross section of the nickel manganese composite hydroxide.

For example, a plurality of nickel manganese composite hydroxideparticles (secondary particles) can be embedded in resin or the like,and through cross-section polisher processing or the like, can be putinto a state such that the cross section can be observed. The particlesize of the fine primary particles and the plate shaped or needle shapedprimary particles can be found by measuring as the maximum diameter ofthe cross section of preferably 10 or more of the primary particles inthe secondary particle, and calculating the average.

Moreover, the ratio of the thickness of the outer shell section withrespect to the particle size of the secondary particles can be found asdescribed below. From among the secondary particles in the resin above,particles in the center whose cross section can be observed areselected, and at three or more arbitrary locations, the distance betweentwo points where the distance from the outer surface of the outer shellsection to the inner surface on the center section side is the shortestis measured, and the average thickness of the outer shell section foreach particle is found. By taking the maximum distance between twoarbitrary points on the outer surface of the secondary particle to bethe particle size of the secondary particle, and dividing the averagethickness by the particle size of the secondary particle, the ratio ofthe thickness of the outer shell section with respect to the particlesize is found for each particle. Furthermore, by averaging the ratiosthat were found for 10 or more particles, it is possible to find theratio of the thickness of the outer shell section with respect to theparticle size of the secondary particles for the nickel manganesecomposite hydroxide particles above.

(Average Particle Size)

The average particle size of the composite hydroxide particles of thepresent invention is adjusted to be 3 to 7 μm, and preferably 3.5 to 6.5μm, and more preferably 4.0 to 5.5 μm. By making the average particlesize 3 to 7 μm, the cathode active material that is obtained using thecomposite hydroxide particles of the present invention as raw materialcan be adjusted to have a specified average particle size (2 to 8 μm).The particle size of the composite hydroxide particles is correlatedwith the particles size of the cathode active material that is obtained,so affects the characteristics of a battery that uses this cathodeactive material as the cathode material.

More specifically, when the average particle size of the compositehydroxide particles is less than 3 μm, the average particle size of theobtained cathode active material also becomes small, and the packingdensity of the cathode decreases, and the battery capacity per volumedecreases. On the other hand, when the average particle size of thecomposite hydroxide particles exceeds 7 μm, specific surface area of thecathode active material decreases, and by reducing the electrolyteinterface the cathode resistance increases, and the outputcharacteristics of the battery decreases.

(Particle Size Distribution)

The composite hydroxide particles of the present invention are adjustedso that the index [(d90−d10)/average particle size)] that indicates theextent of the particle size distribution is 0.55 or less, and preferably0.52 or less, and more preferably 0.50 or less.

The particle size distribution of the cathode active material is greatlyaffected by the composite hydroxide particles, which are the rawmaterial, so when fine particles or coarse particles are mixed with thecomposited hydroxide particles, similar particles also exist in thecathode active material. In other words, when [(d90−d10)/averageparticle size)] exceeds 0.55 and the extent of the particle sizedistribution is large, fine particles or coarse particles also exist inthe cathode active material.

When the cathode is formed using cathode active material in where thereare many fine particles, there is a possibility that heat will begenerated due to localized reaction of the fine particles, and togetherwith a decrease in the safety of the battery, the fine particlesselectively deteriorate, so the cyclability of the battery becomes poor.On the other hand, when the cathode is formed using cathode activematerial in which there are many large particles, there is notsufficient reaction area between the electrolyte and the cathode activematerial, and the output of the battery decreases due to an increase inthe reaction resistance.

Therefore, the composite hydroxide particles of the present inventionare adjusted so that [(d90−d10)/average particle size] is 0.55 or less,and the range of particle size distribution of the cathode activematerial that is obtained by using these composite hydroxide particlesas raw material becomes small, so it is possible to make the particlesize uniform. In other words, the particle size distribution of cathodeactive material can be adjusted such that [(d90−d10)/average particlesize] is 0.60 or less. As a result, in a battery in which cathode activematerial that is formed using the composite hydroxide particles of thepresent invention is used as the cathode material, it is possible toachieve good cyclability and high output.

In the index [(d90−d10)/average particle size] that indicates the extentof the particles size distribution, d10 is the particle size when thenumber of particles of each particle size from the side of smallparticle size is cumulatively totaled, and that accumulated volume is10% of the total volume of all particles. Moreover, d90 is the particlesize when the number of particles is similarly totaled, and thataccumulated volume is 90% the total volume of all particles.

The method for finding the average particle size, d90 and d10 is notparticularly limited, however, for example, they can be found from thevolume integrated value that is measured using a laser diffractionscattering particle size analyzer. When d50 is used as the averageparticle size, it is possible to use the particle size when, as in thecase of d90, the accumulated volume is 50% the entire particle volume.

(Particle Composition)

The composite hydroxide particles of the present invention are adjustedso that the composition is expressed by the following generalexpression. By manufacturing a lithium nickel manganese composite oxidewith a nickel manganese composite hydroxide having the this compositionas the raw material, and when using an electrode having that lithiumnickel manganese composite oxide as the cathode active material in abattery, not only is it possible to lower the value of the measuredcathode resistance, but it is also possible to improve the batteryperformance.

General Expression: Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a)

(x+y+z+t=1, 0.3≦x≦0.7, 0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, 0≦a≦0.5, M is oneor more additional element selected from among Mg, Ca, Al, Ti, V, Cr,Zr, Nb, Mo and W.)

When cathode active material with composite hydroxide particles as theraw material is obtained, the composition ratio (Ni:Mn:Co:M) of thecomposite hydroxide particles is maintained in the obtained cathodeactive material. Therefore, the composition ratio of the compositehydroxide particles of the present invention is adjusted so as to be thesame as the composition ratio that is required for the cathode activematerial to be obtained.

(1-2) Method for Manufacturing Nickel Manganese Composite HydroxideParticles

The method for manufacturing the composite hydroxide particles of thepresent invention is a method for manufacturing nickel manganesecomposite hydroxide particles by a crystallization reaction, andcomprises: a) a nucleation step for performing nucleation, and b) aparticle growth step that grows the nucleus that was produced in thenucleation process.

In other words, in the conventional continuous crystallization method,the nucleation reaction and the particle growth reaction proceededsimultaneously in the same tank, so the particle size distribution ofthe obtained composite hydroxide particles was over a wide range. On theother hand, a feature of the manufacturing method for the compositehydroxide particles of the present invention, is that by clearlyseparating the time when nucleation reaction occurs (nucleation step)and the time when the particle growth reaction occurs (particle growthstep) a narrow particle size distribution is achieved for the obtainedcomposite hydroxide particles.

Moreover, in the present invention, a feature of the nucleation step andthe particle growth step is the use of an aqueous solution that does notsubstantially contain a complex ion formation agent for forming complexions with nickel, manganese and cobalt. In the case of obtaining nickelmanganese complex hydroxide particles by crystallization, normally, acomplex ion formation agent, for example an ammonium ion donor such asammonia aqueous solution, for forming complex ions with nickel,manganese, cobalt and the like put into the solution, however, in thepresent invention, this kind of complex ion formation agent is not used.By not using a complex ion formation agent, the solubility of nickel,manganese and cobalt into the reaction solution in the nucleation stepdecreases, and fine primary particles are generated. Moreover, thecomplex ion formation agent is not used in order to avoid difficulty incontrolling the crystallization due to fluctuation in density caused bythe volatilization of the complex ion formation agent duringcrystallization, and secondarily, in order to reduce the load of thedrainage process.

In addition to an ammonium ion donor as the complex ion formation agentfor forming complex ions with nickel, manganese and cobalt, acetic acid,citric acid and the like that form chelate complex ions with thesemetals are possible.

First, a summary of the method for manufacturing the composite hydroxideparticles of the present invention will be explained based on FIG. 1. InFIG. 1 and FIG. 2, (A) corresponds to the nucleation step and (B)corresponds to the particle growth step.

(Nucleation Step)

As illustrated in FIG. 1, first, a plurality of metallic compoundscontaining at least nickel and manganese are dissolved in water atspecified ratios, to make the mixed aqueous solution. In the method formanufacturing the composite hydroxide particles of the presentinvention, the composition ratio of the metal in the obtained compositehydroxide particles is as a rule the same as the composition ratio ofthe metals in the mixed aqueous solution.

Therefore, the mixed aqueous solution is made by adjusting the ratio ofthe metal compounds to be dissolved in water, mainly nickel, manganeseand cobalt, so that the composition ratio of the metals in the mixedaqueous solution is the same composition ratio as the metals in thecomposite hydroxide particles of the present invention. The addedelements can be coated over the hydroxide particles in a later step, soin that case the composition ration of the metals in the mixed aqueoussolution can be adjusted in consideration of the elements added later.Moreover, the temperature inside the reaction tank is kept at a fixedtemperature, so the mixed aqueous solution should be added after beingheated to a temperature of 25 to 50° C., and preferably after beingheated to 30 to 45° C. When the temperature is less than 25° C., thedifference with the temperature in the tank is large, and it becomesdifficult to control the temperature in the tank. Moreover, when thetemperature exceeds 50° C., the total amount of heat generated resultingfrom the heat brought by the mixed aqueous solution, the heat generateddue to neutralization in the tank, and the heat generated due tofriction heat by mixing becomes large, and temperature inside the tankbecomes higher than the set temperature.

On the other hand, alkali aqueous solution, such as sodium hydroxideaqueous solution, and water are supplied to the reaction tank and mixedto form an aqueous solution that does not substantially contain acomplex ion formation agent that forms complex ions with nickel,manganese and cobalt. This aqueous solution (hereafter, referred to asthe “aqueous solution before reaction”) is heated with steam or hotwater that passes through the jacket and adjusted so that thetemperature is 60° C. or greater, and the pH value is adjusted to bewithin the range 11.5 to 13.5 at a standard solution temperature of 25°C. by adjusting the amount of alkali aqueous solution that is supplied.The pH value of the aqueous solution in the reaction tank can bemeasured using a typical pH meter.

Here, the meaning of “does not substantially contain” means that theamount contained is less than any amount that would having any effect onthe solubility of the metal compounds above in the reaction solution,and the allowed amount differs depending on the kind of complex ionformation agent, however, for example, in the case of ammonium ions,preferably the amount is 1 g/L or less, and more preferably, 0.5 g/L orless, and even more preferably, 0.1 g/L or less. In the case of acetateions, preferably the amount is 3.5 g/L or less, and more preferably, 1.8g/L or less, and even more preferably 0.35 g/L. In any case, it isparticularly preferred that the amount cannot be detected by normalanalysis. When the amount of this kind complex ion formation agent thatis contained in the aqueous solution for nucleation exceeds the allowedamount, the solubility of nickel and cobalt increases, so the depositionrate of composite hydroxides decreases and it becomes easy for primaryparticles to grow, so it becomes impossible to form a nucleus in whichfine primary particles are aggregated, or in other words, it becomesimpossible to form a nucleus that will become the center section ofsecondary composite hydroxide particles, and therefore it becomes easyto obtain solid particles.

Moreover, preferably the atmosphere inside the reaction tank is adjustedso that the oxygen concentration is 10 volume % or less. Controllingthis atmosphere can be adjusted by using an inert gas such as nitrogenor argon. More specifically, adjustment is possible by adjusting theflow rate of air and inert gas in the atmospheric gas that flows intothe reaction tank beforehand so that the oxygen concentration becomes aspecified level, and causing a fixed amount of atmospheric gas tocirculate.

In the reaction tank, after the atmosphere, and the temperature and pHof the aqueous solution before reaction have been adjusted, the mixedaqueous solution is supplied to the reaction tank while stirring theaqueous solution before reaction. As a result, the aqueous solutionbefore reaction is mixed with the mixed aqueous solution, and thus anaqueous solution for nucleation, which is the reaction solution for thenucleation step, is formed, and a minute nucleus of composite hydroxideis formed in the aqueous solution for nucleation. At this time, thetemperature and pH of the aqueous solution for nucleation are within therange above, so the formed nuclei do not grow much, and generation ofthe nuclei has priority.

The pH value of the aqueous solution for nucleation changes duringformation of the nuclei due to the supply of mixed aqueous solution, soalkali aqueous solution is supplied together with mixed aqueous solutionto the aqueous solution for nucleation, and the pH of the aqueoussolution for nucleation is controlled so that the pH value at a standardsolution temperature of 25° C. is kept within the range 11.5 to 13.5.Moreover, the temperature is controlled so that it is kept at 60° C. orhigher.

By supplying mixed aqueous solution and alkali aqueous solution to theaqueous solution for nucleation, new nuclei are continuously generatedin the aqueous solution for nucleation. After a specified number ofnuclei are generated in the aqueous solution for nucleation, thenucleation step ends. Whether or not the specified number of nuclei hasbeen generated is determined according to the amount of metal salt addedto the aqueous solution for nucleation.

(Particle Growth Step)

After the nucleation step has finished, the atmosphere inside thereaction tank is maintained and the temperature is kept at 60° C. orgreater, and the pH of the aqueous solution for nucleation at a standardsolution temperature of 25° C. is adjusted to 9.5 to 11.5, andpreferably, to 9.5 to 11.0, so that pH value is lower than the pH valueduring the nucleation step, and an aqueous solution for particle growth,which is the reaction aqueous solution for the particle growth step, isobtained. More specifically, controlling the pH during this adjustmentis performed by adjusting the amount of alkali aqueous solution that issupplied.

By keeping the pH value of the aqueous solution for particle growthwithin the range above, the growth reaction of the nuclei occurs withpriority over the formation reaction of nuclei, so in the particlegrowth step, hardly any new nuclei are formed in the aqueous solutionfor particle growth, and the nuclei are grown (particle growth) andcomposite hydroxide particle having a specified particle size areformed.

Similarly, as particles are grown by supplying mixed aqueous solution,the pH value of the aqueous solution for particle growth changes, so thepH value of the aqueous solution for particle growth is controlled bysupplying alkali aqueous solution together with mixed aqueous solutionto the aqueous solution for particle growth so that the pH value iswithin the range 9.5 to 11.5 at a standard solution temperature of 25°C. After that, at the instant when the composite hydroxide particleshave grown to a specified particle size, the particle growth step ends.The end of the particle growth step can be determined easily frompreliminary testing from the amount of metal salt added to the reactionsolutions in both the nucleation step and particle growth step, and whenfinding the relationship with the obtained particles, from the amount ofmetal salt added in each step.

As described above, in the case of the method for manufacturingcomposite hydroxide particles above, formation of nuclei takesprecedence in the nucleation step with hardly any nucleus growthoccurring, however, in the particle growth step only nucleus growthoccurs, and hardly any new nuclei are formed. Therefore, in thenucleation step it is possible to form homogeneous nuclei having anarrow particle size distribution range, and in the particle growthprocess, it is possible to homogeneously grow nuclei. Consequently, inthe method for manufacturing composite hydroxide particles, it ispossible to obtain homogeneous nickel manganese composite hydroxideparticles having a narrow particle size distribution range.

In the case of the manufacturing method above, in both steps, metallicions crystallize as nuclei or composite hydroxide particles, so theratio of the liquid component to the metallic component in the reactionsolutions increases. In that case, apparently, the density of the mixedaqueous solution that is supplied is decreased, and particularly in theparticle growth step, there is a possibility that composite hydroxideparticles will not grow sufficiently.

Therefore, preferably, in order to suppress the increase of liquidcomponent, part of the liquid component in the aqueous solution forparticle growth is drained to outside the reaction tank after thenucleation step ends and during the particle growth step. Morespecifically, the supply of mixed aqueous solution and alkali aqueoussolution to the aqueous solution for particle growth and mixing isstopped, the nuclei and composite hydroxide particles are caused toprecipitate out, and the supernatant liquid of the aqueous solution forparticle growth is drained out. As a result, it is possible to increasethe relative concentration of mixed aqueous solution in the aqueoussolution for particle growth. Then, with the relative concentration ofthe mix aqueous solution high, it is possible to grow compositehydroxide particles, so it is possible to make the particle sizedistribution of the composite hydroxide particles even narrower, andthus it is also possible to increase the density of the compositehydroxide particles as secondary particles.

Moreover, in the embodiment illustrated in FIG. 1, after the nucleationstep ends, an aqueous solution for particle growth is formed byadjusting the pH of the aqueous solution for nucleation, and thenparticle growth step is performed after the nucleation step, so there isan advantage in that it is possible to quickly change to the particlegrowth step. Furthermore, there is the advantage that changing from thenucleation step to the particle growth step can be performed easily bysimply adjusting the pH of the reaction solution, and adjusting the pHcan also be performed easily by temporarily stopping the supply ofalkali aqueous solution. In the case of using an inorganic acid that isthe same kind as the acid of the metallic compounds, for example,sulfate, the pH of the reaction solution can also be adjusted by addingsulfuric acid to the reaction solution.

However, in another embodiment as illustrated in FIG. 2, separate fromthe aqueous solution for nucleation, a component adjustment solutionwhose pH is adjusted to correspond to the particle growth step isformed, and a solution containing the nuclei that were formed in thenucleation step in a separate tank (aqueous solution for nucleation, andpreferably, the aqueous solution from which part of liquid component hasbeen removed) is added to this component adjustment solution to form areaction solution, and the particle growth step can be performed withthis reaction solution as the aqueous solution for particle growth.Similar to the aqueous solution before reaction, the componentadjustment solution in this case does not substantially contain acomplex ion formation agent that forms complex ions with nickel,manganese and cobalt, the temperature of the solution is kept at 60° C.or greater, and the pH value is controlled so that when measured atstandard solution temperature of 25° C. the pH value is 9.5 to 11.5, andis less than the pH value in the nucleation step.

In this case, it is possible to separate the nucleation step andparticle growth step more completely, so the state of the reactionsolution in each step can be taken to be an optimum condition for thestep. Particularly, at the time when the particle growth step starts,the pH of the aqueous solution for particle growth can be taken to bethe optimum condition. Therefore, the range of the particle sizedistribution of the nickel manganese composite hydroxide particles thatare formed in the particle growth step can be narrower and morehomogeneous.

(pH Control)

As described above, in the nucleation step, the pH value of the reactionsolution must be controlled so that at a standard solution temperatureof 25° C. the pH value is within the range 11.5 to 13.5, and preferably,within the range 11.8 to 13.3, and more preferably, within the range12.0 to 13.1. When the pH value exceeds 13.5, the nuclei that are formedare too fine, and there is a problem that the reaction solution becomesa gel. Moreover, when the pH value is less than 11.5, the nucleus growthreaction occurs together with nucleation, so the range of the particlesize distribution of the formed nuclei becomes large, and heterogeneous.In other words, in the nucleation step, by controlling the pH value ofthe reaction solution within the range above, it is possible to suppressnucleus growth, and promote only nucleation, and the formed nuclei arehomogeneous and the particle size distribution range can be kept narrow.

On the other hand, in the particle growth step, the pH value of thereaction solution must be controlled so that at a standard solutiontemperature of 25° C. the pH value is within the range 9.5 to 11.6, andpreferably, within the range 9.5 to 11.0, and more preferably, withinthe range 10.0 to 10.6. When the pH value exceeds 11.5, the amount ofnewly formed nuclei increases, and fine secondary particles are formed,so hydroxide particles having a good particle size distribution cannotbe obtained. Moreover, when the pH value is less than 9.5, thesolubility of nickel is high, and the amount of metal ions that remainin the solution without precipitating out increases, so productionefficiency becomes poor. In other words, in the particle growth step, bycontrolling the pH of the reaction solution within the range above, itis possible to cause only growth of the nuclei formed in the nucleationstep to occur and suppress the formation of new nuclei, and thus theobtained nickel manganese composite hydroxide particles are homogeneousand the particle size distribution range can be kept narrow.

In both the nucleation step and the particle growth step, preferably therange of fluctuation of the pH is kept within the set value ±0.2. Whenthe range of fluctuation of the pH is large, nucleation and particlegrowth do not become fixed, and there is a possibility that uniformmanganese composite hydroxide particles having a narrow particle sizedistribution range will not be obtained.

When the pH value is 11.5, this pH value is the boundary conditionbetween nucleation and nucleus growth, so, depending on whether or notthere are nuclei in the reaction solution, this pH value will become thecondition for the nucleation step or the particle growth step. In otherwords, after the pH value for the nucleation step is made to be greaterthan 11.5 a large quantity of nuclei are formed, when the pH value forthe particle growth step is made to be 11.5, there is a large quantityof nuclei in the reaction solution, so nucleus growth occurs withpriority, and hydroxide particles have a narrow particle sizedistribution and relative large particle size are obtained.

On the other hand, when there are no nuclei in the reaction solution, orin other words, when the pH value during the nucleation step is 11.5,there are no nuclei that have grown, so the formation of nuclei takesprecedence, and by lowering the pH value of the particle growth step tobe less than 11.5, the nuclei that are formed grow and good hydroxideparticles are obtained.

In either case, the pH value of the particle growth step should becontrolled to be a value that is less than the pH value in thenucleation step, and in order to clearly separate nucleation fromparticle growth, the pH value of the particle growth step is preferablyat least 0.5 less than the pH value of the nucleation step, and evenmore preferably at least 1.0 less.

(Nucleation Amount)

The amount of nuclei formed during the nucleation step is notparticularly limited, however, in order to obtain composite hydroxideparticles having good particle size distribution, preferably the amountis 1% to 2% of the total volume, or in other words the amount of allmetal salts supplied to obtain the composite hydroxide particles, andmore preferably 1.5% or less. As described above, the amount ofnucleation can be controlled by finding through preliminary testing therelationship between the amount of metal salts added to the reactionsolution and the amount of nuclei obtained.

(Controlling the Particle Size of Composite Hydroxide Particles)

The particle size of the composite hydroxide particles above can becontrolled by the time of the particle growth step, so by continuing theparticle growth step until the particles have been grown to a desiredparticle size, it is possible to obtain composite hydroxide particleshaving a desired particle size.

Moreover, the particle size of the composite hydroxide particles can becontrolled not only by the particle growth step, but also by the pHvalue of the nucleation step and the amount of raw material added fornucleation. In other words, by making the pH value during nucleation thehigh pH value side, or by increasing the amount of raw material added byincreasing the nucleation time, number of nuclei formed is increased. Asa result, even when the particle growth conditions are kept the same, itis possible to make the particle size of the composite hydroxideparticles small. On the other hand, by performing control to reduce thenumber of nuclei formed, it is possible to increase the particle size ofthe obtained composite hydroxide particles.

The shape and size of the primary particles can be controlled bycontrolling the temperature and pH value as described above. Forexample, of the particles of the secondary particles, in order to madethe average particle size of the fine primary particles of the nuclei0.01 to 0.3 μm, the temperature of the nucleation step is controlled tobe 60° C. or greater. On the other hand, in order to make the primaryparticles of the outer shell section plate shaped or needle shaped bycrystallizing around the nuclei in the particle growth step, and makethe average particle size 0.3 to 3 μm, the pH of the particle growthstep is controlled to be 9.5 or greater.

Furthermore, in order to make the thickness of the outer shell sectionbe within the range 0.3 to 3 μm, control is performed to make thesolubility high. Also, in order to make the ratio of the thickness ofthe outer shell with respect to the particle size of the secondaryparticles 10 to 45%, the amount of crystallization is controlled at atemperature of 60° C. or greater, and a pH of 9.5 to 12.

In the following, the conditions for the metallic compounds, reactiontemperature and the like are explained, however, the difference betweenthe nucleation step and the particle growth step is just the range forcontrolling the pH of the reaction solutions, with the conditions suchas the metallic compounds, reaction temperature and the like essentiallybeing the same in both steps.

(Nickel, Manganese and Cobalt Sources)

Compounds containing the target metals are used as the metal sources fornickel, manganese and cobalt. The compounds used are preferablycompounds that are water soluble such as nitrates, sulfates andhydrochlorates. From the aspect of mixing into the hydroxide particles,and disposing of the waste liquid, preferably sulfates, such as nickelsulfate, manganese sulfate and cobalt sulfate are used.

(Added Element Sources)

Preferably, compounds that are water soluble are used as the sources ofthe added elements (one or more element is selected from among theelements Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo and W); for example, titaniumsulfate, ammonium peroxotitanic, titanium potassium oxalate, vanadiumsulfate, ammonium vanadate, chromium sulfate, potassium chromate,zirconium sulfate, niobium oxalate, ammonium molybdate, sodiumtungstate, ammonium tungstate, and the like can be used,

When uniformly dispersing the added elements inside the compositehydroxide particles, it is possible to precipitate out the addedelements into the composite hydroxide particles in a uniformly dispersedstate by adding additives that contain the added elements.

Moreover, when covering the surface of the composite hydroxide particleswith the added elements, for example, by forming a slurry of compositehydroxide particles in an aqueous solution that includes the addedelements, and performing control so that the pH becomes a specifiedvalue, then adding an aqueous solution that includes one or more kind ofadded element and depositing the added elements onto the surface of thecomposite hydroxide particle by a crystallization reaction, it ispossible to uniformly cover the surface with the added elements. In thiscase, it is also possible to use an alkoxide solution added elementsinstead of an aqueous solution containing added elements. Furthermore,it is also possible to cover the surface of the composite hydroxideparticles with added elements by spraying the composite hydroxideparticles with an aqueous solution or slurry containing the addedelements, and drying the liquid. Moreover, the surface can be covered bya method of spraying and drying a slurry in which the compositehydroxide particles and salt including one or more added element aresuspended, or mixing a composite hydroxide and salt containing one ormore added element using a solid-phase method.

When covering the surface with added elements, by reducing the atomicratios of the added element that exist in the mixed solution by just theamount of covering, it is possible to match the atomic ratios with theatomic ratios of the metal ions of the obtained composite hydroxideparticles. The step of covering the surface of the particles with addedelements can also be performed for the particles after the compositehydroxide particles have been heated.

(Mixed Solution Concentration)

Preferably, the concentration of the mixed solution is 1 to 2.6 mol/Lfor the total metallic compounds, and preferably 1.5 to 2.2 mol/L. Whenthe concentration of the mixed solution is less than 1 mol/L, the amountof crystallization per reaction tank decreases, so productivitydecrease, which is not preferable.

On the other hand, when the salt concentration of the mixed solutionexceeds 2.6 mol/L, the concentration exceeds the saturated concentrationat normal temperature, so crystals are reprecipitated and there is adanger that piping of the equipment will become blocked.

Moreover, the metallic compounds do not need to be supplied to thereaction tank as a mixed solution, and, for example, when using metalliccompounds that are formed by reacting when mixed, separate metalliccompound solutions can be prepared and the individual solutions ofmetallic compounds can be supplied at the same time to the reaction tankso that total concentration of metallic compound solution is within therange above.

Furthermore, that amount of mixed solution or amount of individualmetallic compound solutions that are supplied to the reaction tankshould be such that the concentration of crystallization at the timethat the crystallization reaction ends is generally 30 to 200 g/L, andpreferably 80 to 150 g/L. When the concentration of crystallizedmaterial is less than 30 g/L, there is insufficient aggregation ofprimary particles, and when the concentration exceeds 200 g/L, the mixedsolution that is added is not sufficiently dispersed inside the reactiontank, so there is a possibility that there will be deviation in particlegrowth.

(Reaction Temperature)

In the reaction tank, it is necessary to adjust the reaction temperatureto be 60° C. or greater, and preferably 60 to 90° C., and particularlyit is preferred that the temperature be adjusted to be 60 to 80° C. Withthe reaction temperature being within this range, it is possible todissolve the necessary amount of nickel, manganese and cobalt metals forthe crystallization reaction at the proper and fixed solubility withouthaving to add a complex ion formation agent. When the reactiontemperature is less than 60° C., the temperature is low, so thesolubility of nickel, manganese and cobalt becomes too low, it becomesfor nuclei to be formed, and there is a tendency for it to becomedifficult to control the reaction. Even when the temperature is above90° C., the crystallization reaction is possible, however, watervaporization is accelerated, so control of the reaction becomesdifficult, and from an industrial aspect, the cost and safety risk ofmaintaining a high temperature increases, which is not preferable.

In order to keep the reaction temperature at 60° C. or greater, it ispreferable in the nucleation step that both the aqueous solution beforereaction and the reaction solution be 25 to 50° C., and more preferably30 to 45° C. Moreover, in the particle growth step as well, continuingfrom the nucleation step, it is preferable that the temperature of thereaction solution be maintained at 60° C. or greater, and that thetemperature of the added mixed solution be 25 to 50° C., and morepreferably 30 to 45° C.

(Alkali Aqueous Solution)

In regards to the alkali aqueous solution that is used to adjust the pHof the reaction solution, as long as the solution is not a solution thatforms complex ions with nickel, manganese and cobalt, the solution isnot particularly limited; for example, it is possible to use an alkalimetal hydroxide aqueous solution such as sodium hydroxide, potassiumhydroxide an the like, however, from the aspect of cost and ease ofhandling, sodium hydroxide is preferred. In the case of alkali metalhydroxide, it is possible to supply that alkali metal hydroxide directlyto the reaction solution, however, from the aspect of ease of controlthe pH of the reaction solution in the reaction tank, adding the alkalimetal hydroxide to the reaction solution in the reaction tank as anaqueous solution is preferred.

The method for adding the alkali aqueous solution to the reaction tankis also not particularly limited, and can be added using a pump capableof flow control, such as a constant rate pump, while sufficientlystirring the reaction solution so that the pH value of the reactionsolution is kept within the specified range.

(Atmosphere During Crystallization)

In the nucleation step, from the aspect of suppressing oxidation ofcobalt and manganese and stably forming particles, preferably the oxygenconcentration of the space inside the reaction tank must be controlledto 10% by volume or less, and more preferably, 5% by volume or less, andeven more preferably, 1% by volume or less. Even in the particle growthstep it is important to control oxidation, and it is necessary tosimilarly control the oxygen concentration of the space inside thereaction tank. The oxygen concentration of the atmosphere can beadjusted, for example, using an inert gas such as nitrogen, argon or thelike. It is possible to constantly cause a fixed amount of atmosphericgas to circulate inside the atmosphere as a method for adjusting theoxygen concentration inside the atmosphere to a specified concentration.

(Crystallization Time)

The crystallization times in the nucleation step and the particle growthstep are appropriately selected according to the target particle size ofthe composite hydroxide particles. For example, when trying to obtainsecondary particles that are within the specified range of the presentinvention by using a mixed solution (1.8 mol/L) of nickel sulfate andmanganese sulfate and a sodium hydroxide solution (25% by volume), thenucleation step is preferably 20 seconds to 4 minutes, and the particlegrowth step is preferably 3 to 4 hours. When the nucleation step is lessthan 20 seconds, it is not possible to form a sufficient amount ofnuclei, and when the nucleation step exceeds 4 minutes, too many nucleiare formed, so a problem occurs in that there is variation in theparticle size due to aggregation. On the other hand, when the particlegrowth step is less than 3 hours, there is not enough time for particlegrowth, so it becomes difficult to control the particle size, and it isnot possible to obtain uniform secondary particles. When the particlegrowth step exceeds 4 hours, the average particle size of the secondaryparticles exceeds the desired range, and a problem occurs in thatproductivity decreases. From the aspect of productivity, preferably thenucleation step is 30 seconds to 3 minutes 30 seconds, and the particlegrowth step is 3 hours 30 seconds to 4 hours.

(Manufacturing Equipment)

In the method for manufacturing composite hydroxide particles of thepresent invention, an apparatus is used that does not collect theproduced material until the reaction is complete. For example, theapparatus is a typically used batch reaction tank in which a mixerprovided. When using this kind of apparatus, a problem of collectinggrowing particles at the same time as the overflow liquid, such asoccurs in a continuous crystallization apparatus that collects theproduced material by a typical overflow, does not occur, so it ispossible to obtain particles having a narrow particle size distributionand uniform particle size.

Moreover, preferably the reaction atmosphere is controlled, so using anapparatus, such as a sealed apparatus, that is capable of atmospherecontrol is preferred. By using such an apparatus, it is possible tomanufacture composite hydroxide particles having the structure above,and it is possible to uniformly promote the nucleation reaction andparticle growth reaction, so it is possible to obtain particles having agood particle size distribution, or in other words, particles having anarrow particle size distribution range.

(2-1) Cathode Active Material for a Non-Aqueous Electrolyte SecondaryBattery

The cathode active material of the present invention is lithium nickelmanganese composite oxide particles that are represented by the generalformula: Li_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂ (where −0.05≦u≦0.50),x+y+z+t=1, 0.3≦x≦0.7, 0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, and M is at leastone kind of added element selected from among Mg, Ca, Al, Ti, V, Cr, Zr,Nb, Mo and W), and has a layered hexagonal crystal structure. A cathodeactive material having a layered hexagonal crystal structure, itadvantageous in that when compared with a cathode active material havinga spinel structure, has excellent theoretical capacity density, andcyclability.

(Composition)

The cathode active material of the present invention is lithium nickelmanganese composite oxide particles, and the composition thereof isadjusted so as to satisfy the general formula above.

In the cathode active material of the present invention, “u”, whichindicates the surplus amount of lithium, is within the range −0.5 to0.50. When the surplus amount “u” of lithium is less than −0.05, thereaction resistance of the cathode of the non-aqueous electrolytesecondary battery that uses the obtained cathode active material becomeslarge, so the output of the battery becomes low. On the other hand, whenthe surplus amount “u” of lithium exceeds 0.50, the initial dischargecapacity when the cathode active material above is used for the cathodeof the battery decreases, and the reaction resistance of the cathodealso increases. In order to further reduce the reaction resistance,preferably the surplus amount “u” of Lithium is no less 0.10 and nogreater than 0.35.

Moreover, the nickel (Ni), manganese (Mn) and cobalt (Co), together withthe Li, make up the basic structure of the lithium-containing compositeoxide having layered hexagonal crystal structure. The atomic ratios “x”,“y”, “z” that indicate the amounts contained of these elements aredetermined for the non-aqueous electrolyte secondary battery that usesthe obtained cathode active material in consideration of batterycapacity, cyclability and safety. The value of “x” is 0.3 to 0.7, andpreferably 0.33 to 0.65; the value of “y” is 0.1 to 0.55, and preferably0.2 to 0.5; and the value of “z” is 0.4 or less, and preferably 0.35 orless.

As expressed in the general formula above, the cathode active materialof the present invention is preferably adjusted so that the lithiumnickel manganese composite oxide particles contain added element(s) M.By containing element(s) M above, it is possible to improve thedurability, and output characteristics of a battery that uses thiscathode active material.

Particularly, by uniformly distributing the added element on the surfaceor inside the particles, it is possible to obtain the above effect inthe whole of the respective particles, and together with obtaining theeffect above by adding a small amount, it is possible to suppress adecrease in capacity. Furthermore, in order to obtain the effect byadding an even smaller amount, preferably the concentration of addedelement on the surface is higher than that inside the particles.

When the atomic ratio “t” of the added element(s) M with respect to allmetal atoms (Ni, Mn, Co and added element(s) M) exceeds 0.1 the metalelements that contribute to the Redox reaction decrease, so the batterycapacity decreases, which is not preferred. Therefore, the addedelement(s) M is adjusted so that the atomic ratio is within the rangeabove.

(Average Particle Size)

The cathode active material of the present invention has an averageparticle size of 2 to 8 μm. When the average particle size is less than2 μm, the packing density of particles when the cathode is formeddecreases, and the battery capacity per volume of the cathode decreases.On the other hand, when the average particle size exceeds 8 μm, thespecific surface area of the cathode active material decreases, and bythe interface with the electrolyte of the battery decreasing, theresistance of the cathode increases and the output characteristic of thebattery decreases.

Therefore, by adjusting the cathode active material so that the averageparticle size is preferably 2 to 8 μm, or more preferably 3 to 6.5 μm,it is possible to increase the battery capacity per volume of thebattery that uses this cathode active material for the cathode, and itis possible to obtain excellent battery characteristics such as safetyand high output.

(Particle Size Distribution)

As illustrated in FIG. 7, for the cathode active material compriseshighly homogeneous lithium nickel manganese composite oxide secondaryparticles having an index [(d90−d10)/average particle size] thatindicates the size of the particle distribution of 0.60 or less, and anaverage particle size of 2 to 8 μm.

For the cathode active material of the present invention, the index[(d90−d10)/average particle size] that indicates the size of theparticle size distribution is 0.60 or less, and preferably 0.55 or less,and even more preferably 0.52 or less.

When particle size distribution is wide, there are many fine particleshaving a particle size that is very small with respect to the averageparticle size, or coarse particles having a particle size that is verylarge with respect to the average particle size. When the cathode isformed using a cathode active material having many fine particles, thereis a possibility that heat will be generated due to localized reactionof the fine particles, and together with a decrease in safety, fineparticles selectively deteriorate, causing the cyclability to becomepoor. However, when the cathode is formed using cathode active materialhaving many coarse particles, there is not sufficient reaction area forthe electrolyte and cathode active material, and thus the battery outputdecreases due to an increase in reaction resistance.

Therefore, by making the index [(d90−d10)/average particle size]described above 0.60 or less, it is possible to reduce the ratio of fineparticles or coarse particles in the particle size distribution ofcathode active material, and a battery that uses this cathode activematerial for the cathode is very safe, and has good cyclability andbattery output characteristics. The average particle size, d90 and d10are the same as those used for the composite hydroxide particles, andmeasurement is performed in the same way.

(Particle Structure)

As illustrated in FIG. 8, a feature of the cathode active material ofthe present invention is the hollow structure comprising a hollowsection inside the secondary particles and an outer shell section on theoutside. By having this kind of hollow structure, it is possible toincrease the reaction area, and electrolyte enter inside from theparticle boundaries or space between the primary particles of the outershell, and lithium is inserted and removed at the reactive interface onthe surface of the primary particles on the hollow side inside theparticles as well, so mobility of Li ions and electrons is not hindered,and it is possible to increase the output characteristic.

In the present invention, the thickness of the outer shell section iswithin the range 0.5 to 2.5 μm. Preferably the range is 0.5 to 2 μm, andit is particularly preferred that the range be 0.6 to 1.8 μm. When thethickness of the outer shell section is less than 0.5 μm, the hollowsection becomes too large, packing into the electrode becomes worse, thestrength of the secondary particles is insufficient, and duringformation of the electrode, the particles are broken and become fine;and when the thickness of the outer shell section exceeds 2.5 μm, thehole connecting with the hollow section are covered by the particles ofthe outer shell section, so a problem occurs in that the hollowstructure cannot be taken advantage of and the characteristics decrease.

Moreover, preferably the ratio of the thickness of the outer shellsection with respect to the particle size is 5 to 45% and morepreferably, 5 to 38%. When the ratio of the thickness of the outer shellsection with respect to the particle size is less than 5%, the strengthof the lithium nickel manganese composite oxide particles decreases, sohandling the powder, and when used in a battery cathode, the particlesbreak down and become fine particles, making the characteristics poor.On the other hand, when the ratio of the thickness of the outer shellsection with respect to the particle size exceeds 45%, only a smallamount of electrolyte enters inside the hollow section inside theparticles from the particle boundaries and spaces, and the surface areathat contributes to the battery reaction becomes smaller, so the cathoderesistance increases and the output characteristic decreases.

The thickness of the outer shell section of lithium nickel manganesecomposite oxide particles and the ratio of the thickness of the outershell section with respect to the particle size can be found in the sameways as for the composite hydroxide particles.

(Specific Surface Area)

In the case of the cathode active material of the present invention, thespecific surface area is 1 to 2 m²/g, and preferably 1.2 to 1.8 m²/g.When the specific surface area is 1 m²/g or greater, the reaction areaof the cathode active material and the electrolyte is sufficientlylarge, so a battery that uses a cathode that is formed suing thiscathode active material can become a high-output battery. On the otherhand, when the specific surface area is too large, the particle sizebecomes to small, and the amount of active material that can be chargedinside a battery having limited volume is reduced, and the capacity pervolume of the battery decreases. Therefore, for the cathode activematerial of the present invention, the upper limit for the specificsurface area is taken to be 2 m²/g.

(Characteristics)

When the cathode active material above is used for example in thecathode of a 2032 type coin battery, when cobalt is not added, highinitial discharge capacity of 200 mAh/g or greater is obtained, and evenwhen cobalt is added at an atomic ratio of 30% of the entire metallicelements other than lithium, a high initial discharge capacity of 150mAh/g is obtained, and low cathode resistance and high cycle capacityretention is obtained, which are excellent characteristics for a cathodeactive material for a non-aqueous electrolyte secondary battery.

(2-2) Method for Manufacturing Cathode Active Material for a Non-AqueousElectrolyte Secondary Battery

As long as the method for manufacturing the cathode active material ofthe present invention is such that the cathode active material has theaverage particle size, particle size distribution and particle structureabove, the method is not particularly limited, however, by employing themethod below the cathode active material can surely be manufactured, sois preferred.

As illustrated in FIG. 3, the method for manufacturing cathode activematerial of the present invention includes: a) a step of heat treatingthe nickel manganese composite hydroxide particles that are the rawmaterial for the cathode active material of the present inventionobtained and obtained by the manufacturing method above; b) a mixingstep for forming a mixture by mixing a lithium compound into theparticles after heat treatment; and a calcination step of calcining themixture that was formed in the mixing step. Each of the steps will beexplained below.

a) Heat Treatment Step

The heat treatment step is a step for performing heat treatment thatheats the nickel manganese composite hydroxide particles (hereafter,referred to as composite hydroxide particles) to a temperature of 105 to750° C., and removes the moisture contained in the composite hydroxideparticles. By performing this heat treatment step, the moisture thatremains in the particles until the calcination step can be reduced to acertain amount. As a result, it is possible to prevent fluctuation inthe percentage of the number of metal atoms or the number of lithiumatoms in the manufactured cathode active material.

Moisture should be removed to an amount such that fluctuation in thepercentage of the number of metal atoms or the number of lithium atomsin the manufactured cathode active material does not occur, so it is notabsolutely necessary to convert all of the composite hydroxide particlesto nickel manganese composite oxide particles (hereafter, referred to ascomposite oxide particles). However, in order to further reduce thefluctuation described above, preferably the heating temperature is 500°C. or greater, and all of the composite hydroxide particles areconverted to composite oxide particles.

In the heat treatment step, when the heating temperature is less the105° C., it is not possible to remove the surplus moisture in thecomposite hydroxide particles, and it is not possible to suppress thefluctuation above. On the other hand, when the heating temperatureexceeds 750° C., the particles are sintered by the heat treatment, andit is not possible to obtain composite oxide particles having a uniformparticle size. The metallic component that is included in the compositehydroxide particles is analyzed according to the heat treatmentconditions and found beforehand, and by determining a ratio with thelithium compound, it is possible to suppress the fluctuation.

The atmosphere for performing heat treatment is not particularlylimited, and can be a non-reducing atmosphere, however, preferably heattreatment is performed in an atmosphere wherein air flow can beperformed easily.

Moreover, the heat treatment time is not particularly limited, however,when the time is less than one hour, the removal of surplus moisture inthe composite hydroxide particles cannot be performed sufficiently, sopreferably the time is one hour or longer, and more preferably 5 to 15hours.

The equipment that is used in the heat treatment is not particularlylimited, and as the composite hydroxide particles can be heated in anon-reducing atmosphere, and preferably in air flow, an electric furnacethat does not generate gas can suitably be used.

b) Mixing Step

The mixing step is a step for obtaining a lithium mixture by mixing thecomposite hydroxide particles that were heat treated in the heattreatment step (hereafter, referred to as heat treated particles) with amaterial containing lithium, for example a lithium compound.

Here, not only the composite hydroxide particles from which residualmoisture was removed in the heat treatment step, but also complex oxideparticles that were converted to oxides in the heat treatment step or amixture of these particles is contained in the heat treated particles.

The heat treated particles and the lithium compounds are mixed so thatthe ratio of the number of lithium atoms with respect to the number ofmetal atoms other than lithium in the lithium mixture, in other words,the sum of the atoms of nickel, manganese, cobalt and added elements(Me) (Li/Me) is 0.95 to 1.5, and preferably 1 to 1.5, and morepreferably 1.1 to 1.35. In other words, the ratio Li/Me does not changebefore and after the calcination step, so the ratio Li/Me in the mixingstep become the ratio Li/Me in the cathode active material, so mixing isperformed so that the ratio Li/Me of the lithium compound is the same asthe ratio Li/Me in the cathode active material to be obtained.

The lithium compound that is used for forming the lithium mixture is notparticularly limited, however, for example, from the aspect of the easeof obtaining material, lithium hydroxide, lithium sulfate, lithiumcarbonate or a mixture of these is preferred. Particularly, taking intoconsideration the ease of handling and the stability of quality,preferably lithium hydroxide or lithium carbonate is used.

Preferably the lithium mixture is sufficiently mixed before calcination.When mixing is not sufficient, there is a possibility that problems willoccur such as fluctuation in Li/Me between individual particles, andsufficient battery characteristics will not be obtained.

Furthermore, a typical mixer can be used for mixing; for example, it ispossible to use a shaker mixer, V blender, ribbon mixer, Julia mixer,Loedige mixer or the like, and the composite oxide particles should besufficiently mixed with material containing lithium to an extent thatthe framework of the heat treated particles is not broken down. Forexample, in the case of using a shaker mixer, by setting the mixingcondition to be 5 to 20 minutes, it is possible to sufficiently mix thecomposite hydroxide particles and lithium compound.

c) Calcination Step

The calcination step is a step that calcinates the lithium mixture thatwas obtained in the mixing step, and forms a hexagonal crystal typelayered lithium nickel manganese composite oxide. When the lithiumcompound is calcinated in the calcination step, the lithium in a lithiumcontaining material is dispersed in the heat treated particles, so alithium nickel manganese composite oxide is formed.

(Calcination Temperature)

The calcination of the lithium mixture is preferably performed at atemperature of 800 to 980° C., and more preferably 820 to 960° C.

When the calcination temperature is less than 800° C., dispersion oflithium into the heat treated particles is not performed sufficiently,and surplus lithium or unreacted particles remain, the crystal structureis not sufficiently arranged, and when used in a battery, sufficientbattery characteristics are not obtained.

Moreover, when the calcination temperature exceeds 980° C., there is apossibility that together with severe sintering occurring betweencomposite oxide particles, there will be abnormal particle growth, sothere is a possibility that the particles after calcination will becomecoarse, and it will not be possible to maintain the particle shape(spherical particles shape to be described next). In the case of thiskind of cathode active material, the specific surface area decreases, sowhen used in a battery, there is a problem in that the cathoderesistance increases and the battery capacity decreases.

From the aspect of uniformly performing the reaction between the heattreated particles ad the lithium compound, preferably the temperatureabove will rise at a temperature increase rate of 3 to 50° C./min.Furthermore, by maintaining the temperature at near the melting point ofthe lithium compound for 1 to 5 hours, it is possible to perform a evenmore uniform reaction.

(Calcination Time)

Of the calcination time, the hold time, during which the temperature ismaintained at a specified temperature, is preferably at least one hour,and more preferably 2 to 12 hours. When the time is less than one hour,it is possible that the formation of the lithium nickel manganesecomposite oxide will not be performed sufficiently. After this hold timeis finished, the time is not particularly limited, however, when thelithium mixture is accumulated in a sagger and calcinated, in order toprevent deterioration of the sagger, preferably the atmosphere is cooledto 200° C. at a cooling rate of 2 to 10° C./min.

(Temporary Calcination)

Particularly, when lithium hydroxide or lithium carbonate is used as thelithium compound, temporary calcination is performed by maintaining thetemperature at a temperature of 350 to 800° C., which is lower than thecalcination temperature, and preferably at a temperature of 450 to 780°C. for 1 to 10 hours, and preferably 3 to 6 hours. In other words,preferably temporary calcination is performed at the reactiontemperature of the lithium hydroxide or lithium carbonate and the heattreated particles. In this case, by maintaining the temperature at nearthe reaction temperature of the lithium hydroxide or lithium carbonate,it is possible to sufficiently perform dispersion of the lithium intothe heat treated particles, and thus it is possible to obtain uniformlithium nickel manganese composite oxide.

When it is desired to increase the concentration of added element M onthe surface of the lithium nickel manganese composite oxide particles,heat treated particles of the raw material, the surface of which areuniformly covered by the added element M, can be used. By calcining alithium mixture that contains the heat treated particles under moderateconditions, it is possible to increase the concentration of the addedelement M on the surface of the lithium nickel manganese composite oxideparticles. More specifically, by calcining a lithium mixture thatcontains heat treated particles covered by the added element M at atemperature lower than the calcination temperature and for a timeshorter than the calcination time, it is possible to obtain lithiumnickel manganese composite particles having an increased concentrationof added element M on the surface of the particles. For example, whenthe calcination temperature is taken to be 800 to 900° C. and thecalcination time is 1 to 5 hours, it is possible to increase theconcentration of added element M on the surface of the particles by 1 to10%.

On the other hand, even when a lithium mixture containing heat treatedparticles covers with the added element M is calcinated, when thecalcination temperature is high and the calcination time is long, it ispossible to obtain lithium nickel manganese composite oxide particles inwhich the added element is uniformly distributed inside the particles.In other words, by adjusting the heat treated particles of the rawmaterial and the calcination conditions, it is possible to obtainlithium nickel manganese composite oxide particles having the targetconcentration distribution.

(Calcination Atmosphere)

The calcination atmosphere is preferably an oxidizing atmosphere, andmore preferably the oxygen concentration is 18 to 100% by volume, and amixed atmosphere of oxygen having the oxygen concentration describedabove and an inert gas is particularly preferred. In other words,preferably calcination is performed in atmospheric air or in an oxygenflow. When the oxygen concentration is less than 18% by volume, there isa possibility that the crystallinity of the lithium nickel manganesecomposite oxide will not be sufficient. Particularly, when consideringthe battery characteristics, performing calcination in oxygen flow ispreferred.

The furnace that is used in calcination is not particularly limited, andas long as the lithium mixture can be heated in atmospheric air or inoxygen flow any kind of furnace can be used, however, from the aspect ofuniformly maintaining the atmosphere inside the furnace, a furnace inwhich gas is not generated is preferred, it is possible to used either abatch type or continuous type of furnace.

(Cracking)

Of the lithium nickel manganese composite oxide particles obtained bycalcination, aggregation or light sintering may occur. In that case, theparticles must be cracked, and as a result, lithium nickel manganeseoxide, or in other words, the cathode active material of the presentinvention can be obtained. Cracking is an operation for loosening up anaggregate wherein mechanical energy is applied to an aggregate of aplurality of secondary particles resulting from sintering neckingbetween secondary particles during calcination in order to separate thesecondary particles without breaking drown the secondary particlesthemselves. As the method of cracking, it is possible to use a knownmethod such as a pin mill, hammer mill or the like, however, whenperforming cracking, the cracking force should preferably be adjusted sothat the secondary particles are not broken down.

(3) Non-Aqueous Electrolyte Secondary Battery

The non-aqueous electrolyte secondary battery of the present inventionemploys a cathode that uses the cathode active material for anon-aqueous electrolyte secondary battery for the cathode. First, theconstruction of the non-aqueous electrolyte secondary battery of thepresent invention will be explained.

Except for using cathode active material of the present invention, theconstruction of the non-aqueous electrolyte secondary battery of thepresent invention essentially comprises the same construction as atypical non-aqueous electrolyte secondary battery.

More specifically, the secondary battery of the present inventioncomprises a case, a cathode and anode that are housed in the case, anon-aqueous electrolyte and a separator. Even more specifically, anelectrode unit that is obtained by layering a cathode and electrode witha separator in between is impregnated with a non-aqueous electrolyte,and collector leads are used to connect between the cathode currentcollector of the cathode and the cathode terminal that leads to theoutside, and between the anode current collector of the anode and theanode terminal that leads to the outs, and these are sealed in the caseto form the secondary battery of the present invention.

The construction of the secondary battery of the present invention,needless to say, is not limited to the example above, and various shapescan be used for the external shape such as a can shape, layered shape orthe like.

(Cathode)

First, the cathode, which is the feature of the secondary battery of thepresent invention, is explained. The cathode is a sheet shaped member,and is formed, for example, by coating and drying a blended cathodematerial paste that contains the cathode active material of the presentinvention on the surface of an aluminum foil collector.

The cathode is appropriately process to correspond to the type ofbattery used. For example, processing such as a cutting process to forma suitable size for the battery, a compression process such as rollpressing or the like to increase the electrode density and the like isperformed.

The blended cathode material paste is formed by adding a solvent to theblended cathode material and mixing them. The blended cathode materialis formed by mixing the powder cathode active material of the presentinvention with a conductive material and a binding agent.

The conductive material is added for giving suitable conductivity to theelectrode. This conductive material is not particularly limited, forexample, a carbon black material such as graphite (natural graphite,man-made graphite, expanded graphite), acetylene black, Ketchen blackand the like can be used.

The binding agent serves the role of binding cathode active materials.The binding agent that is used in this blended cathode material is notparticularly limited, however, it is possible to use, for example,polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE),fluororubber, ethylene-propylene-diene rubber, styrene-butdiene,cellulose resin, polyacrylic acid or the like.

It is also possible to add activated carbon to the blended cathodematerial, and by added activated carbon, it is possible to increase theelectric double layer capacitance of the cathode.

The solvent dissolves the bonding agent, and causes the cathode activematerial, conductive material and activated carbon to be dispersed intothe bonding agent. This solvent is not particularly limited, however, itis possible use an organic solvent such as N-methyl-2-pyrrolidone forexample.

The mixture ratio of the material inside the blended cathode materialpaste is not particularly limited. For example, when the solid contentof the blended cathode material without the solvent is taken to be 100parts by weight, then as in the case of a cathode in a typicalnon-aqueous electrolyte secondary battery, the content of the cathodeactive material can be 60 to 95 parts by weight, the content of theconductive material can be 1 to 20 parts by weight, and the content ofthe binding agent can be 1 to 20 parts by weight.

(Anode)

The anode is a sheet shaped member that is formed by coating and dryingblended anode material paste on the surface of a metal foil collectormade of metal such as copper. This anode is formed essentially by thesame method as the cathode, however the components of the blended anodematerial paste, the composition of those components, and the material ofthe collector differ, and as in the case of the cathode, variousprocessing is performed as necessary.

The blended anode material paste is formed by adding a suitable solventto the blended anode material, which is a mixture of anode activematerial and a binding agent, to obtain a paste.

The anode active material, for example, can be a material containinglithium such as metallic lithium or lithium alloy, or can be anabsorbing material that is capable of absorption and desorption oflithium ions.

The absorbing material is not particularly limited, and it is possibleto use natural graphite, man-made graphite, an organic compound firedmaterial such as phenol resin and the like, or a powder like carbonmaterial such as coke. When this absorbing material is used for theanode active material, as in the case of the cathode, it is possible touse a fluorine-containing resin such as PVDF as the binding agent, andit is possible to use an organic solvent such as N-methyl-2-pyrrolidoneas the solvent that disperses the anode active material into the bindingagent.

(Separator)

The separator is located between the cathode and the anode, andfunctions to separate the cathode and anode and to hold the electrolyte.The separator is made from a thin polyethylene or polypropylene film,for example, it is possible to use a film having a plurality of fineholes, however, as long as the separator has the functions describedabove, it is not particularly limited.

(Non-Aqueous Electrolyte)

The non-aqueous electrolyte is formed by dissolving a lithium salt,which is the supporting electrolyte salt, in an organic solvent.

The organic solvent can be selected from one kind or a mixture of two ormore kinds of a cyclic carbonate such as ethylene carbonate, propylenecarbonate, butylene carbonate, trifluoroacetic propylene carbonate orthe like; a chain carbonate such as diethyl carbonate, dimethylcarbonate, ethyl methyl carbonate, dipropyl carbonate and the like, anether compound such as tetrahydrofuran, 2-methyltetrahydrofuran,dimethoxyethane and the like; a sulfur compound such as ethyl methylsulfone, butane sultone and the like; or a phosphorus compound such astriethyl phosphate, trioctyl phosphate and the like.

As the supporting electrolyte salt, it is possible to use a salt such asLiPF₆, LiBF₄, LiClO₄, LiAsF₆, LiN(CF₃SO₂)₂ or a combination of these.

In order to improve the battery characteristics, the non-aqueouselectrolyte can also include a radical scavenger, a surfactant, a flameretardant and the like.

(Characteristics of the Non-Aqueous Electrolyte Secondary Battery of thePresent Invention)

The non-aqueous electrolyte secondary battery of the present inventionis constructed as described above, and has a cathode that uses thecathode active material of the present invention, so a high initialdischarge capacity of 150 mAh/g or greater, and preferably 155 mAh/g,and a low cathode resistance of 10Ω or less, and preferably 9Ω or lessare obtained, so the battery is a high capacity and high output battery.Moreover, the ability to maintain a 200 cycle capacity is 80% orgreater, and preferably 85% or greater, so has excellent cyclability,and when compared with conventional lithium, can be said to have highthermal stability and good safety characteristics.

(Uses of the Secondary Battery of the Present Invention)

The secondary battery of the present invention has the abovecharacteristics, so it is suitable for use as a power source for acompact portable device that requires constant high capacity (such as anotebook personal computer, mobile telephone or the like).

Moreover, the secondary battery of the present invention is alsosuitable for use as battery as the power source for driving a motor thatrequires high output. As a battery becomes large, it becomes difficultto maintain safety, and expensive protective circuits are essential,however, the secondary battery of the present invention has excellentsafety, so not only is it easy to maintain safety, it is possible tosimplify expensive protective circuits, and further lower the cost. Thebattery can be made to be compact and have high output, so is suitableas a power source for conveying equipment that is restricted byinstallation space.

EXAMPLES Example 1 Manufacturing of the Composite Hydroxide Particles

The composite hydroxide particles were manufactured as described below.For all samples, the composite hydroxide particles, cathode activematerial and secondary battery were manufactured using high gradespecimens manufactured by Wako Pure Chemical Industries, Ltd.

(Nucleation Step)

First, 7 liters of water is put into the reaction tank (34 L) and whilestirring, the temperature inside the tank is set to 70° C., and nitrogengas is caused to be circulated for 30 minutes, and the oxygenconcentration in the space inside the reaction tank is kept at 1% orless. An appropriate amount of 25% by volume sodium hydroxide aqueoussolution is added to the water in the reaction tank, and the pH value ofthe aqueous solution in the reaction tank before reaction is adjusted toa value of 13.1 at a standard solution temperature of 25° C.

Next, nickel sulfate and manganese sulfate is dissolved in the water toprepare a ⅛ mol/L mixed solution. The mixed solution is adjusted so thatthe elemental mole ratio of each metal is Ni:Mn=50:50.

This mixed solution is added at a rate of 88 ml/min to the aqueoussolution in the reaction tank before reaction to form a reactionsolution. At the same time, 25% by volume sodium hydroxide aqueoussolution is also added at a constant rate to the reaction solution, andwhile circulating nitrogen gas though the reaction solution, and whileperforming control to keep the pH value of the reaction solution(aqueous solution for nucleation) at a value of 13.1 (nucleation pHvalue), nucleation was performed by allowing crystallization for 2minutes 30 seconds. The range of fluctuation of the pH value was ±0.2.Moreover, the temperature inside the tank was maintained at 60° C. orgreater.

(Particle Growth Step)

After nucleation ended, the temperature inside the tank was maintainedat 60° C. or greater, and sulfuric acid was added until the pH value ofthe reaction solution reached a value of 10.6 at a standard solutiontemperature of 25° C. After the pH value of the reaction solutionreached 10.6, the mixed solution and the 25% by volume sodium hydroxideaqueous solution were one again supplied to the reaction solution(aqueous solution for particle growth), and while performing control tokeep that pH value at 10.6 at a standard solution temperature of 25° C.,crystallization was performed for 4 hours. The grown material was thenwashed, filtered and dried to obtain composite hydroxide particles.

During the crystallization above, the pH was controlled using a pHcontroller to adjust the supply flow rate of sodium hydroxide aqueoussolution, and the range of fluctuation was within the range of ±0.2 ofthe set value.

[Analysis of the Composite Hydroxide]

For the obtained composite hydroxide, after a sample was dissolved in aninorganic acid, chemical analysis was performed by using ICP-AtomicEmission Spectrometry, and the composition was found to beNi_(0.5)Mn_(0.5)(OH)_(2+a) (0≦a≦0.5).

Moreover, for this composite hydroxide, the value [(d90−d10)/averageparticle size] that indicates the average particle size and particlessize distribution is calculated and found from the volume integratedvalue that was measured using a laser diffraction scattering particlesize distribution measurement device (Microtrac HRA, manufactured byNikkiso Co., Ltd.). As a result, the average particle size was found tobe 3.9 μm, and the value [(d90−d10)/average particle size] was 0.49.

Next, SEM (scanning electron microscope S-4700, manufactured by HitachiHigh-Technologies Corporation) observation (magnification rate: 1000×)of the obtained composite hydroxide particles was performed, and it wasconfirmed that the composite hydroxide particles were spherical, and theparticle size was nearly uniform. The SEM observation results areillustrated in FIG. 5.

A sample of the obtained composite hydroxide particles is embedded inresin, and after performing a cross-section polishing process, SEMobservation was performed at a magnification rate of 10,000×, and as aresult it was found that the composite hydroxide particles comprisessecondary particles, and those secondary particles were spherical inshape with a center section having fine primary particles with aparticle size of 0.05 μm, and an outer shell section having plate shapedor needle shaped primary particles having a particle size of 0.8 μm wereobserved, with the thickness of the outer shell section being 1.2 μm.The results of the SEM observation of this cross section are illustratedin FIG. 6. The thickness of the outer shell section with respect to thediameter of the secondary particles was found to be 30.8% from the SEMobservation of this cross section.

[Manufacturing the Cathode Active Material]

The composite hydroxide particles were heat treated in air (oxygen: 21%by volume) at a temperature of 700° C. for 6 hours, converted tocomposite oxide particles and recovered.

Lithium hydroxide was weighed so that Li/Me=1.35, and then mixed withthe composite oxide particles above to prepare a lithium mixture. Mixingwas performed using a shaker mixer (TURBULA Type T2C, manufactured byWilly A. Bachofen (WAB)).

The obtained lithium mixture was temporarily calcinated in air (oxygen:21% by volume) at a temperature of 500° C. for 4 hours, then calcinatedat 900° C. for 4 hours, cooled, and then crushed to obtain the cathodeactive material.

[Analysis of the Cathode Active Material]

Using the same method as for the composite hydroxide particles, theparticle size distribution of the obtained cathode active material wasmeasured, and the average particle size was 4.3 μm, and the value[(d90−d10)/average particle size] was 0.55.

Using the same method as for the composite hydroxide particles, the SEMobservation and cross-section SEM observation of the cathode activematerial were performed, and it was confirmed that the obtained cathodeactive material was spherical and the particle size was mostly uniform.The results of the SEM observation of this cathode active material isillustrated in FIG. 7. On the other hand, it was also confirmed from thecross-section SEM observation that this cathode active material hashollow construction comprising an outer shell section of sinteredprimary particles, and a hollow section inside the shell section. Thethickness of the outer shell section was 0.66 μm. The results of thecross-section SEM observation of this cathode active material areillustrated in FIG. 8. The ratio of the thickness of the outer shellsection with respect to the particle size of the cathode active materialwas 15.3%.

The specific surface area of the obtained cathode active material wasfound using a flow type gas adsorption specific surface area measurementdevice (Multisorb, manufactured by Yuasa-Ionics) to be 1.5 m²/g.

Moreover, analysis by Cu—Kα line powder X-ray diffraction was performedfor the obtained cathode active material using an X-ray diffractometer(X'Pert PRO, manufactured by PANalytical), and the crystal structure ofthe cathode active material was confirmed to comprise a single-phasehexagonal layered crystal lithium nickel manganese composite oxide.

Furthermore, similarly, using the ICP-Atomic Emission Spectrometrymethod, the composition of the cathode active material was analyzed, andconfirmed to be Li_(1.36)Ni_(0.50)Mn_(0.50)O₂ with a composition of Liat 9.55% by weight, Ni at 29.7% by weight and Mn at 27.8% by weight.

[Manufacturing the Secondary Battery]

For evaluation of the obtained cathode active material, the cathodeactive material was used in 2032 type coin battery. As illustrated inFIG. 9, this coin type battery 1 comprises a case 2, and electrodes 3that are housed inside the case 2.

The case 2 has a cathode can 2 a that is hollow and opened on one end,and an anode can 2 b that is placed at the opening section of thecathode can 2 a, and when this anode can 2 b is placed at the openingsection of the cathode can 2 a, a space is formed that houses electrodes3 between the anode can 2 and cathode can 2 a.

The electrodes 3 comprise a cathode 3 a, separator 3 c and anode 3 b,which are layered in this order, and are housed in the case 2 such thatthe cathode 3 a comes in contact with the inner surface of the cathodecan 2 a, and the anode 3 b comes in contact with the inner surface ofthe anode can 2 b.

The case 2 comprises a gasket 2 c, and this gasket 2 c fastens thecathode can 2 a and anode can 2 b so that an electrically insulatedstate is maintained between the cathode can 2 a and anode can 2 b.Moreover, the gasket 2 c also has the function of sealing off the spacebetween the cathode can 2 a and anode can 2 b and closing off the spacebetween the inside of the case 2 and the outside so that the space isairtight and fluid tight.

This coin type battery 1 is manufactured as described below. First, 52.5mg of the obtained cathode active material, 15 mg of acetylene black,and 7.5 mg of polytetrafluoroethylene resin (PTFE) are mixed, and thenthe cathode 3 a is manufactured by pressing the mixture with a pressureof 100 MPa, to a diameter of 11 m and length of 100 μm. The manufacturedcathode 3 a is dried in a vacuum drier at 120° C. for 12 hours. Usingthis cathode 3 a, an anode 3 b, a separator 3 c and electrolyte, thecoin type battery 1 is manufactured inside a glove box having an Aratmosphere having a dew point controlled at −80° C.

An anode sheet that is formed by coating copper foil with graphitepowder having an average particle size of 20 μm and polyvinylidenefluoride and that is punched into a disk shape having a diameter of 14mm is used as the anode 3 b. A porous polyethylene film having a filmthickness of 25 μm is used as the separator 3 c. A mixed solution(manufactured by Tomiyama Pure Chemical Industries, Ltd.) of equalamounts of ethylene carbonate (EC) and diethyl carbonate (DEC) with 1Mof LiClO₄ as the supporting electrolyte is used as the electrolyte.

[Battery Evaluation]

The initial discharge capacity, the cycle capacity retention rate andthe cathode resistance, which are used to evaluate the performance ofthe obtained coin type battery, are defined in the following.

The initial discharge capacity is the capacity after the coin typebattery 1 is allowed to sit for 24 hours after being manufactured andthe open circuit voltage (OCV) has become stable, is charged to a cutoffvoltage of 4.8 V with the current density with respect to the cathodebeing 0.1 mA/cm², then after stopping for one hour, is discharged to acutoff voltage of 2.5 V.

The cycle capacity retention rate is the calculated ratio of thedischarge capacity after the charging/discharging cycle of charging to4.5 V and discharging to 3.0 V has been performed 200 times, with thecurrent density with respect to the cathode being 2 mA/cm², and theinitial discharge capacity. Measurement of the charge and dischargecapacity is performed using a multi-channel voltage/current generator(R6741A, manufactured by Advantest Corporation).

The cathode resistance is evaluated as described below. The coin typebattery 1 is charged to a potential of 4.1 V, an then using a frequencyresponse analyzer and a potentio/galvanostat (1255B, manufactured bySolartron), the cathode resistance is measured by the alternatingcurrent impedance method, and a Nyquist plot as illustrated in FIG. 10is obtained. This Nyquist plot is represented as a sum of characteristiccurves that indicated the solution resistance, anode resistance andcapacity, and cathode resistance and capacity, so the value of thecathode resistance was calculated by performing a fitting calculationusing an equivalent circuit based on this Nyquist plot.

In performing battery evaluation of the coin type battery having acathode that was formed using the cathode active material above theinitial charge capacity was 206.5 mA/g, and the cathode resistance was8.3Ω. The capacity retention rate was 86% after 200 cycles.

The characteristics of the composite hydroxide obtained in this exampleis illustrated in Table 1, and the characteristics of the cathode activematerial and the evaluations of a coin type battery that uses thiscathode active material are illustrated in Table 2. The same contentsfor examples 2 to 4 and comparative examples 1 to 3 below are alsoillustrated in Table 1 and Table 2.

Example 2

Except for mixing lithium hydroxide and composite oxide particles weremixed so that Li/Me=1.25, and using a calcination temperature of 850°C., cathode active material for a non-aqueous electrolyte secondarybattery was obtained in the same way as in Example 1.

The average particle size of the cathode active material was 4.8 μm, thevalue [(d90−d10)/average particle size] was 0.52 and the specificsurface area was 1.6 m²/g. Moreover, it was confirmed from SEMobservation that the cathode active material was spherical and theparticle size was mostly uniform, and comprised a outer shell section ofsintered primary particles and a hollow section on the inside thereof.From this observation it was found that the thickness of the outer shellsection of the cathode active material was 0.58 μm and the ratio of thethickness of the outer shell section with respect to the particle sizewas 14.1%. Furthermore, it was confirmed that the crystal structure ofthe cathode active material was single-phase hexagonal layeredcrystalline lithium nickel manganese composite oxide, with thecomposition of the cathode active material being expressed asLi_(1.25)Ni_(0.50)M_(0.50)O₂, where Li is 8.84% by weight, Ni is 29.9%by weight and Mn is 28.0% by weight.

The same battery evaluation as in Example 1 was performed for a cointype battery having a cathode that is formed using the cathode activematerial above, and it was found that the initial discharge capacity was202.3 mAh/g, and the cathode resistance was 8.9Ω. Moreover, the capacityretention rate after 200 cycles was 85%.

Example 3

Except for using a 1.8 mol/L mixed solution that was obtained by settingthe temperature in the reaction tank to 65° C., adjusting the pH valueof the reaction solution to 12.8 at a standard solution temperature of25° C., dissolving nickel sulfate, cobalt sulfate, manganese sulfate andzirconium sulfate in water so that the molar ratio of the metal elementswas Ni:Co:Mn Zr=33.2:33.1:33.3:0.5 and controlling the pH value of thereaction solution during the nucleation step to a value of 12.8, thecomposite hydroxide particles were obtained in the same way as inExample 1.

The composition of the composite hydroxide particles is expressed asNi_(0.332)Cu_(0.331)Mn_(0.332)Zr_(0.005)(OH)_(2+a) (0≦a≦0.5), theaverage particle size was 3.8 μm, and the value [(d90−d10)/averageparticle size] was 0.41. From SEM observation it was confirmed that thecomposite hydroxide particles were spherical and had mostly a uniformparticle size. Furthermore, it was observed that the composite hydroxideparticles comprised secondary particles, and that the secondaryparticles were spherical with a center section of primary particleshaving a particle size of 0.04 μm and an outer shell section of plateshaped or needle shaped primary particles having a particle size of 0.9μm; the thickness of the outer shell section being 0.95 μm and the ratioof the thickness of the outer shell section with respect to the particlesize being 25%.

Next, except for heat treating the obtained composite hydroxide for 12hours at 150° C., then using lithium carbonate as a lithium compound toobtain a lithium mixture with Li/Me=1.15, and temporarily calcining theobtained lithium mixture in air for 4 hours at 760° C., and performingcalcination for 10 hours at 950° C., cathode active material wasobtained in the same way as in Example 1.

The average particle size of the cathode active material was 4.0 μm, thevalue [(d90−d10)/average particle size] was 0.47, and the specificsurface area was 1.3 m²/g. From SEM observation it was confirmed thatthe cathode active material was spherical, had mostly a uniform particlesize and had hollow structure with an outer shell section comprisingsintered primary particles, and a hollow section inside thereof. Fromthis observation it was found that the thickness of the outer shellsection was 0.92 μm and the ratio of the thickness of the outer shellsection with respect to the particle size was 23%. Furthermore, it wasconfirmed that the crystal structure of this cathode active material wassingle-phase hexagonal layered crystalline lithium nickel manganesecomposite oxide, and that the composition of the cathode active materialwas represented as Li_(1.15)Ni_(0.332)Co_(0.331)Mn_(0.332)Zr_(0.005)O₂,where Li was 7.93% by weight, Ni was 19.2% by weight, Co was 19.3% byweight, Mn was 18.0% by weight and Zr was 0.45% by weight.

When evaluating a coin type battery that has a cathode that was formedusing the cathode active material above, except that the cutoff voltageis made to be 3.0 to 4.3 V, evaluation was performed in the same way asin Example 1, and it was found that the initial discharge capacity was158.2 mAh/g, and the cathode resistance was 3.2Ω. Moreover, the capacityretention rate after 200 cycles was 91%.

Example 4

Except for simultaneously and continuously adding an aqueous solution ofsodium tungstate during the crystallization reaction, the compositehydroxide particles were obtained in the same as in Example 3.

The composition of the composite hydroxide particles is expressed asNi_(0.33)Co_(0.33)Mn_(0.33)Zr_(0.005)W_(0.005)(OH)_(2+a) (0≦a≦0.5), theaverage particle size was 4.0 μm, and the value [(d90−d10)/averageparticle size] was 0.44. From SEM observation, it was confirmed that thecomposite hydroxide particles were spherical and mostly had uniformparticle size. Furthermore, it was observed that the composite hydroxideparticles comprised secondary particles, and that the secondaryparticles were spherical with a center section having primary particleswith a particle size of 0.03 μm and an outer shell section having plateshape or needle shaped primary particles with a particle size of 0.8 μm;the thickness of the outer shell section being 1.0 μm and the ratio ofthe thickness of the outer shell section with respect to the particlesize being 25%.

After that, cathode active material was obtained from the compositehydroxide particles in the same way as in Example 3. The averageparticle size of the cathode active material was 4.3 μm, the value[(d90−d10)/average particle size] was 0.49, and the specific surfacearea was 1.4 m²/g. From SEM observation it was confirmed that thecathode active material was spherical, had mostly a uniform particlesize and had hollow structure with an outer shell section comprisingsintered primary particles, and a hollow section inside thereof. Fromthis observation it was found that the thickness of the outer shellsection was 0.95 μm and the ratio of the thickness of the outer shellsection with respect to the particle size was 22%. Furthermore, it wasconfirmed that the crystal structure of this cathode active material wassingle-phase hexagonal layered crystalline lithium nickel manganesecomposite oxide, and that the composition of the cathode active materialwas represented asLi_(1.15)Ni_(0.33)Cu_(0.33)Mn_(0.33)W_(0.005)Zr_(0.005)O₂, where Li was8.07% by weight, Ni was 19.6% by weight, Co was 19.7% by weight, Mn was18.3% by weight, Zr was 0.46% by weight and W was 0.93% by weight.

A coin type battery that has a cathode that was formed using the cathodeactive material above was evaluated in the same way as in Example 3, andit was found that the initial discharge capacity was 157.4 mAh/g, andthe cathode resistance was 3.1Ω. Moreover, the capacity retention rateafter 200 cycles was 92%.

Example 5

Except for using a 1.8 mol/L mixed solution obtained by dissolvingnickel sulfate, cobalt sulfate, manganese sulfate and zirconium sulfatein water so that the molar ratio of each metal element was Ni:Co:MnZr=33.2:33.1:33.2:0.5, and simultaneously and continuously adding anaqueous solution of sodium tungstate during the crystallizationreaction, the composite hydroxide particles were obtained in the same asin Example 1.

The composition of the composite hydroxide particles is expressed asNi_(0.33)Cu_(0.33)Mn_(0.33)Zr_(0.005)W_(0.005)(OH)_(2+a) (0≦a≦0.5), theaverage particle size was 3.8 μm, and the value [(d90−d10)/averageparticle size] was 0.42. From SEM observation, it was confirmed that thecomposite hydroxide particles were spherical and mostly had uniformparticle size. Furthermore, it was observed that the composite hydroxideparticles comprised secondary particles, and that the secondaryparticles were spherical with a center section having primary particleswith a particle size of 0.03 μm and an outer shell section having plateshape or needle shaped primary particles with a particle size of 0.8 μm;the thickness of the outer shell section being 1.0 μm and the ratio ofthe thickness of the outer shell section with respect to the particlesize being 26.3%.

Next, except for heat treating the obtained composite hydroxide for 12hours at 150° C., then using lithium carbonate as a lithium compound toobtain a lithium mixture with Li/Me=1.15, and temporarily calcining theobtained lithium mixture in air for 4 hours at 760° C., and performingcalcination for 10 hours at 950° C., cathode active material wasobtained in the same way as in Example 1.

The average particle size of the cathode active material was 4.1 μm, thevalue [(d90−d10)/average particle size] was 0.48, and the specificsurface area was 1.3 m²/g. From SEM observation it was confirmed thatthe cathode active material was spherical, had mostly a uniform particlesize and had hollow structure with an outer shell section comprisingsintered primary particles, and a hollow section inside thereof. Fromthis observation it was found that the thickness of the outer shellsection was 0.94 μm and the ratio of the thickness of the outer shellsection with respect to the particle size was 23%. Furthermore, it wasconfirmed that the crystal structure of this cathode active material wassingle-phase hexagonal layered crystalline lithium nickel manganesecomposite oxide, and that the composition of the cathode active materialwas represented asLi_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)Zr_(0.005)W_(0.005)O₂, where Li was8.07% by weight, Ni was 19.6% by weight, Co was 19.7% by weight, Mn was18.3% by weight, Zr was 0.46% by weight and W was 0.93% by weight.

When evaluating a coin type battery that has a cathode that was formedusing the cathode active material above, except that the cutoff voltageis made to be 3.0 to 4.3 V, evaluation was performed in the same way asin Example 1, and it was found that the initial discharge capacity was158.2 mAh/g, and the cathode resistance was 3.2Ω. Moreover, the capacityretention rate after 200 cycles was 92%.

Example 6

Except for adding the aqueous solution for nucleation after thenucleation step to a component adjustment solution that was preparedseparately from the aqueous solution of nucleation to form a reactionsolution and performing the particle growth step with this reactionsolution as the particle growth aqueous solution, the compositehydroxide particles were obtained in the same way as in Example 1. Thecomponent adjustment solution was adjusted to a pH value of 10.6 bymixing a 1.8 mol/L mixed solution that was obtained by dissolving nickelsulfate and manganese sulfate in water with a 25% by weight sodiumhydroxide aqueous solution.

The composition of the composite hydroxide particles is expressed asNi_(0.50)Mn_(0.50)(OH)_(2+a) (0≦a 0.5), the average particle size was4.1 μm, and the value [(d90−d10)/average particle size] was 0.50. FromSEM observation, it was confirmed that the composite hydroxide particleswere spherical and mostly had uniform particle size. Furthermore, it wasobserved that the composite hydroxide particles comprised secondaryparticles, and that the secondary particles were spherical with a centersection having primary particles with a particle size of 0.04 μm and anouter shell section having plate shape or needle shaped primaryparticles with a particle size of 0.9 μm; the thickness of the outershell section being 1.1 μm and the ratio of the thickness of the outershell section with respect to the particle size being 26.8%.

After that the cathode active material was obtained in the same way asin Example 1. The average particle size of the cathode active materialwas 4.3 μm, the value [(d90−d10)/average particle size] was 0.53, andthe specific surface area was 1.2 m²/g. From SEM observation it wasconfirmed that the cathode active material was spherical, had mostly auniform particle size and had hollow structure with an outer shellsection comprising sintered primary particles, and a hollow sectioninside thereof. From this observation it was found that the thickness ofthe outer shell section was 1.1 μm and the ratio of the thickness of theouter shell section with respect to the particle size was 25.6%.Furthermore, it was confirmed that the crystal structure of this cathodeactive material was single-phase hexagonal layered crystalline lithiumnickel manganese composite oxide, and that the composition of thecathode active material was represented asLi_(1.36)Ni_(0.50)Mn_(0.50)O₂, where Li was 9.53% by weight, Ni was29.6% by weight, and Mn was 27.7% by weight.

When evaluating a coin type battery that has a cathode that was formedusing the cathode active material above in the same way as in Example 1,it was found that the initial discharge capacity was 203.3 mAh/g, andthe cathode resistance was 8.6Ω. Moreover, the capacity retention rateafter 200 cycles was 85%.

Example 7

Except for stopping the supply and mixing of the mixed solution andsodium hydroxide aqueous solution once to allow the nuclei and compositehydroxide to precipitate out and drain the supernatant liquid from theparticle growth aqueous solution during the particle growth process, thecomplex hydroxide particles are obtained in the same way as in Example1.

The composition of the composite hydroxide particles is expressed asNi_(0.50)Mn_(0.50)(OH)_(2+a) (0≦a 0.5), the average particle size was3.9 μm, and the value [(d90−d10)/average particle size] was 0.48. FromSEM observation, it was confirmed that the composite hydroxide particleswere spherical and mostly had uniform particle size. Furthermore, it wasobserved that the composite hydroxide particles comprised secondaryparticles, and that the secondary particles were spherical with a centersection having primary particles with a particle size of 0.05 μm and anouter shell section having plate shape or needle shaped primaryparticles with a particle size of 0.9 μm; the thickness of the outershell section being 1.3 μm and the ratio of the thickness of the outershell section with respect to the particle size being 33.3%.

After that the cathode active material was obtained in the same way asin Example 1. The average particle size of the cathode active materialwas 4.3 μm, the value [(d90−d10)/average particle size] was 0.54, andthe specific surface area was 1.4 m²/g. From SEM observation it wasconfirmed that the cathode active material was spherical, had mostly auniform particle size and had hollow structure with an outer shellsection comprising sintered primary particles, and a hollow sectioninside thereof. From this observation it was found that the thickness ofthe outer shell section was 0.7 μm and the ratio of the thickness of theouter shell section with respect to the particle size was 16%.Furthermore, it was confirmed that the crystal structure of this cathodeactive material was single-phase hexagonal layered crystalline lithiumnickel manganese composite oxide, and that the composition of thecathode active material was represented asLi_(1.36)Ni_(0.50)Mn_(0.50)O₂, where Li was 9.55% by weight, Ni was29.7% by weight, and Mn was 27.8% by weight.

When evaluating a coin type battery that has a cathode that was formedusing the cathode active material above in the same way as in Example 1,it was found that the initial discharge capacity was 204.5 mAh/g, andthe cathode resistance was 8.4Ω. Moreover, the capacity retention rateafter 200 cycles was 85%.

Comparative Example 1

Using a reaction tank for continuous crystallization comprising anoverflow pipe at the top, in atmospheric air, crystallization wasperformed by a typical method wherein a mixed solution that is the sameas in Example 1, a 10 g/L ammonia aqueous solution, and 25% by weightsodium hydroxide aqueous solution are continuously added at a constantflow rate while keeping the pH value of the reaction solution constantat 11.0 at a standard solution temperature of 25° C., and theoverflowing slurry is continuously recovered. The temperature inside thetank was maintained as 40° C. Except for setting the average amount oftime inside the reaction tank for 10 hours, recovering the slurry,separating the solids and liquid, and obtaining crystallized matterafter the inside of the tank reached a continuous state of equilibrium,cathode active material for a non-aqueous electrolyte secondary batterywas obtained and evaluated in the same way as in Example 1.

The composition of the composite hydroxide particles is expressed asNi_(0.50)Mn_(0.50)(OH)_(2+a) (0≦a 0.5), the average particle size was10.2 μm, and the value [(d90−d10)/average particle size] was 0.70. FromSEM observation, it was confirmed that overall the composite hydroxideparticles were primary particles that were the same as those of theouter shell section of Example 1.

The average particle size of the cathode active material was 10.5 μm,the value [(d90−d10)/average particle size] was 0.73, and the specificsurface area was 1.4 m²/g. From SEM observation it was confirmed thatthe cathode active material was spherical, had mostly a uniform particlesize and were particles having a dense solid structure. Furthermore, itwas confirmed that the crystal structure of this cathode active materialwas single-phase hexagonal layered crystalline lithium nickel manganesecomposite oxide, and that the composition of the cathode active materialwas represented as Li_(1.36)Ni_(0.50)Mn_(0.50)O₂, where Li was 9.55% byweight, Ni was 29.7% by weight, and Mn was 27.8% by weight.

Evaluation of a battery that was the same as that of Example 1 wasperformed, and it was found that the initial discharge capacity was208.2 mAh/g, and the cathode resistance was 30.5Ω. Moreover, thecapacity retention rate after 200 cycles was 78%.

Comparative Example 2

Except for adding 25% by weight ammonia water during the crystallizationreaction so that the ammonia concentration in the solution becomes 15g/L, keeping the temperature inside the tank at 40° C., making the pHduring nucleation 12.8, and the pH during particle growth 11.6, cathodeactive material for a non-aqueous electrolyte secondary battery wasobtained and evaluated in the same way as in Example 3.

The composition of the composite hydroxide particles is expressed asNi_(0.332)Co_(0.331)Mn_(0.332)Zr_(0.005) (OH)_(2+a) (0≦a 0.5), theaverage particle size was 4.2 μm, and the value [(d90−d10)/averageparticle size] was 0.43. From SEM observation, it was confirmed thatoverall the composite hydroxide particles were primary particles thatwere the same as those of the outer shell section of Example 1.

The average particle size of the cathode active material was 4.4 μm, thevalue [(d90−d10)/average particle size] was 0.51, and the specificsurface area was 0.85 m²/g. From SEM observation it was confirmed thatthe cathode active material was spherical, had mostly a uniform particlesize and were particles having a dense solid structure. Furthermore, itwas confirmed that the crystal structure of this cathode active materialwas single-phase hexagonal layered crystalline lithium nickel manganesecomposite oxide, and that the composition of the cathode active materialwas represented as Li_(1.15)Ni_(0.331)Cu_(0.331)Mn_(0.332)Zr_(0.005)O₂,where Li was 7.93% by weight, Ni was 19.2% by weight, Co was 19.3% byweight, Mn was 18.0% by weight and Zr was 0.45% by weight.

Evaluation of a battery that was the same as that of Example 3 wasperformed, and it was found that the initial discharge capacity was155.6 mAh/g, and the cathode resistance was 5.1Ω. Moreover, the capacityretention rate after 200 cycles was 90%. The particles had a solidstructure, so when compared with the particles in example 3 having thesame composition, the specific surface area was low and the cathoderesistance was high.

Comparative Example 3

Except for the temperature inside the tank being 40° C., the pH duringparticle growth being 11.6, and the calcination conditions being 1050°C. and 10 hours, the composite oxide cathode active material wasobtained in the same way as in Example 3.

The composition of the composite hydroxide particles is expressed asNi_(0.332)Co_(0.331)Mn_(0.332)Zr_(0.005) (OH)_(2+a) (0≦a 0.5), theaverage particle size was 4.0 μm, and the value [(d90−d10)/averageparticle size] was 0.44. From SEM observation, it was confirmed that thecomposite hydroxide particles were spherical and mostly had uniformparticle size. Furthermore, it was observed that the composite hydroxideparticles comprised secondary particles, and that the secondaryparticles were spherical with a center section having primary particleswith a particle size of 0.05 μm and an outer shell section having plateshape or needle shaped primary particles with a particle size of 0.9 μm;the thickness of the outer shell section being 1.0 μm and the ratio ofthe thickness of the outer shell section with respect to the particlesize being 25%.

The average particle size of the cathode active material was 8.9 μm, thevalue [(d90−d10)/average particle size] was 0.92, and the specificsurface area was 0.42 m²/g. From SEM observation it was confirmed thatthe cathode active material was spherical, however, sintering ofsecondary particles advanced forming tertiary particles. It was alsoconfirmed from this observation that sintering of primary particles andparticle growth advanced, and the hollow section became very small. Fromthis observation it was found that the thickness of the outer shellsection of the cathode active material was 2.0 μm and the ratio of thethickness of the outer shell section with respect to the particle sizewas 22.5%. Furthermore, it was confirmed that the crystal structure ofthis cathode active material was single-phase hexagonal layeredcrystalline lithium nickel manganese composite oxide, and that thecomposition of the cathode active material was represented asLi_(1.146)Ni_(0.332)Cu_(0.331)Mn_(0.332)Zr_(0.005)O₂, where Li was 7.80%by weight, Ni was 19.1% by weight, Co was 19.1% by weight, Mn was 17.9%by weight, and Zr was 0.45% by weight.

When evaluating a battery in the same way as for Example 3, it was foundthat the initial discharge capacity was 141.4 mAh/g, and the cathoderesistance was 8.6Ω. Moreover, the capacity retention rate after 200cycles was 76%. The calcination temperature was high and sinteringadvanced, so when compared with the third example having the samecomposition, the specific surface area was low and the cathoderesistance value was high.

TABLE 1 (Manufacturing Conditions and Characteristics of CompositeHydroxide Particles) Average Particle Size of Primary SecondaryParticles Particles Thickness of the Added Tank Particle NH₃ Average(d90-d10)/ Center Outer shell Outer Shell Section Element Temp.Nucleation Growth Concentration particle Size Avg. Particle sectionsection Thickness Rate M (° C.) pH pH (g/L) (μm) Size (μm) (μm) (μm) (%)Example 1 — 70 13.1 10.6 — 3.9 0.49 0.05 0.8 1.2 30.8 Example 2 — 7013.1 10.6 — 3.9 0.49 0.05 0.8 1.2 30.8 Example 3 Zr 65 12.8 10.6 — 3.80.41 0.04 0.9 0.95 25.0 Example 4 Zr, W 65 12.8 10.6 — 4.0 0.44 0.03 0.81.0 25.0 Example 5 Zr, W 70 13.1 10.6 — 3.8 0.42 0.03 0.8 1.0 26.3Example 6 — 70 13.1 10.6 — 4.1 0.50 0.04 0.9 1.1 26.8 Example 7 — 7013.1 10.6 — 3.9 0.48 0.05 0.9 1.3 33.3 Comparative — 40 11.0 11.0 1010.2 0.70 — — Uniform structure Example 1 Comparative — 40 12.8 11.6 154.2 0.43 — — Uniform structure Example 2 Comparative Zr 40 12.8 11.6 —4.0 0.44 0.05 0.9 1.0 25 Example 3

TABLE 2 (Manufacturing Conditions and Characteristics of Cathode ActiveMaterial) Avg. Particle (d90-d10)/ Calcination Size Avg. particle Li/Me(° C.) Composition (μm) size Example 1 1.35 900Li_(1.36)Ni_(0.50)Mn_(0.50)O₂ 4.3 0.55 Example 2 1.25 850Li_(1.25)Ni_(0.50)Mn_(0.50)O₂ 4.8 0.52 Example 3 1.15 950Li_(1.15)Ni_(0.332)Co_(0.331)Mn_(0.332)Zr_(0.005)O₂ 4.0 0.47 Example 41.15 950 Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)Zr_(0.005)W_(0.005)O₂ 4.30.49 Example 5 1.15 950Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)Zr_(0.005)W_(0.005)O₂ 4.1 0.48Example 6 1.35 900 Li_(1.36)Ni_(0.50)Mn_(0.50)O₂ 4.3 0.53 Example 7 1.35900 Li_(1.36)Ni_(0.50)Mn_(0.50)O₂ 4.3 0.54 Comparative 1.35 900Li_(1.36)Ni_(0.50)Mn_(0.50)O₂ 10.5 0.73 Example 1 Comparative 1.15 950Li_(1.15)Ni_(0.332)Co_(0.331)Mn_(0.332)Zr_(0.005)O₂ 4.4 0.51 Example 2Comparative 1.15 1050Li_(1.146)Ni_(0.332)Co_(0.331)Mn_(0.332)Zr_(0.005)O₂ 8.9 0.92 Example 3Outer shell Specific Initial Capacity thickness Surface DischargeCathode Retention Thickness Rate Area Capacity Resistance Rate (μm) (%)(m²g⁻¹) (mAh · g⁻¹) (Ω) (%) Example 1 0.66 15.3 1.5 206.5 8.3 86 Example2 0.58 14.1 1.6 202.3 8.9 85 Example 3 0.92 23 1.3 158.2 3.2 91 Example4 0.95 22 1.4 157.4 3.1 92 Example 5 0.94 23 1.3 158.2 3.2 92 Example 61.1 25.6 1.2 203.3 8.6 85 Example 7 0.7 16 1.4 204.5 8.4 85 ComparativeSolid 1.4 208.2 30.5 78 Example 1 Comparative Solid 0.85 155.6 5.1 90Example 2 Comparative 1.0 22.5 0.42 141.4 8.6 76 Example 3

INDUSTRIAL APPLICABILITY

The non-aqueous electrolyte secondary battery of the present inventionis suitable as a power source for compact electronic devices (notebooktype personal computer, mobile telephone, and the like).

Moreover, the non-aqueous electrolyte secondary battery of the presentinvention has excellent safety characteristics, is compact and has highoutput, so is suitable for use as a power source of conveying equipmentwith limited space.

EXPLANATION OF REFERENCE NUMBERS

-   1 Coin type battery-   2 Case-   2 a Cathode can-   2 b Anode can-   2 c Gasket-   3 Electrodes-   3 a Cathode-   3 b Anode-   3 c Separator

1. A method for manufacturing nickel manganese composite hydroxideparticles by a crystallization reaction such that the nickel manganesecomposite hydroxide particles can be expressed by the general formulaNi_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a)(where x+y+z+t=1, 0.3≦x≦0.7,0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, 0≦a≦0.5, and M is one or more addedelement that is selected from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Moand W), the manufacturing method comprising: a nucleation step ofcontrolling an aqueous solution for nucleation, which includes at leasta metallic compound that contains nickel and a metallic compound thatcontains manganese, and does not include a complex ion formation agentthat forms complex ions with nickel, manganese and cobalt, so that thetemperature of the solution is 60° C. or greater, and so that the pHvalue that is measured at a standard solution temperature of 25° C. is11.5 to 13.5, and generating nuclei as center sections comprising fineprimary particles; and a particle growth step of controlling an aqueoussolution for particle growth, which includes the nuclei that were formedin the nucleation step and does not substantially include a complex ionformation agent that forms complex ions with nickel, manganese andcobalt, so that the temperature of the solution is 60° C. or greater,and so that the pH value that is measured at a standard solutiontemperature of 25° C. is 9.5 to 11.5, and is less than the pH value inthe nucleation step, and growing an outer shell section comprisingprimary particles having a plate shape or needle shape that is largerthan the fine primary particles on an outer surface of the nuclei. 2.The manufacturing method for manufacturing nickel manganese compositehydroxide particles according claim 1 wherein in the nucleation step andparticle growth step, the oxygen concentration inside the reaction tankis controlled to be 10% by volume or less.
 3. The manufacturing methodfor manufacturing nickel manganese composite hydroxide particlesaccording to claim 1 wherein the pH value of the aqueous solution fornucleation after the nucleation step has finished is adjusted and theresulting aqueous solution is used as the aqueous solution for particlegrowth.
 4. The manufacturing method for manufacturing nickel manganesecomposite hydroxide particles according to claim 1 wherein a solutionthat is obtained by adding an aqueous solution, which contains thenuclei formed in the nucleation step, to a component adjustment aqueoussolution, which is separate from the aqueous solution for nucleation inwhich the nuclei were formed, does not substantially include a complexion formation agent that forms complex ions with nickel, manganese andcobalt, and is controlled so that the solution temperature is 60° C. orgreater, and so that the pH value that is measured at a standardsolution temperature of 25° C. is 9.5 to 11.5 and is lower than the pHvalue in the nucleation step, is used as the aqueous solution forparticle growth.
 5. The manufacturing method for manufacturing nickelmanganese composite hydroxide particles according to claim 4, whereinthe particle growth step starts after part of the liquid component ofthe aqueous solution for particle growth has been removed.
 6. Themanufacturing method for manufacturing nickel manganese compositehydroxide particles according to claim 1, wherein the nickel compositehydroxide that was obtained in the particle growth step is covered witha compound containing the one or more added elements.
 7. Nickelmanganese composite hydroxide particles that are expressed by thegeneral formula Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a) (where x+y+z+t=1,0.3≦x—0.7, 0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, 0≦a≦0.5, and M is one or moreadded element that is selected from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb,Mo and W), and that are spherical shaped secondary particles that areformed by a plurality of aggregate primary particles, wherein thesecondary particles have an average particle size of 3 to 7 μm, a value[(d90−d10)/average particle size], which is an index indicating theextent of the particle size distribution, of 0.55 or less, the particleshaving a center section comprising fine primary particles, and an outershell section on the outside of the center section comprising plateshaped or needle shaped primary particles that are larger than the fineprimary particles, with the thickness of the outer shell section being0.3 to 3 μm.
 8. The nickel manganese composite hydroxide particlesaccording to claim 7, wherein the fine primary particles have an averageparticle size of 0.01 to 0.3 μm, and the plate shaped or needle shapedprimary particles that are larger than the fine primary particles havean average particle size of 0.3 to 3 μm.
 9. The nickel manganesecomposite hydroxide particles according to claim 7, wherein the ratio ofthe thickness of the outer shell section with respect to the particlesize of the secondary particles is 10 to 45%.
 10. The nickel manganesecomposite hydroxide particles according to claim 7, wherein the one ormore added elements are uniformly distributed inside the secondaryparticles and/or uniformly cover the surface of the secondary particles.11. (canceled)
 12. A manufacturing method for manufacturing cathodeactive material for a non-aqueous electrolyte secondary batterycomprising lithium nickel manganese composite oxide having layeredhexagonal crystal structure and expressed by the general formula:Li_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂ (where −0.05≦u≦0.50, x+y+z+t=1,0.3≦x≦0.7, 0.1≦y≦0.55, 0≦z≦0.4, 0≦t≦0.1, M is an added element selectedfrom one or more elements from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Moand W), the manufacturing method comprising: a mixing step that mixes alithium compound into the nickel manganese composite hydroxide particlesof claim 7 to form a lithium mixture; and a calcination step thatperforms calcination of the mixture formed in the mixing step in anoxygen atmosphere at a temperature of 800 to 980° C.
 13. Themanufacturing method for manufacturing cathode active material for anon-aqueous electrolyte secondary battery according to claim 12, whereinthe lithium mixture is adjusted so that the ratio of the sum of thenumber of metal atoms other than lithium included in the lithium mixtureand the number of lithium atoms is 1:0.95 to 1.5.
 14. The manufacturingmethod for manufacturing cathode active material for a non-aqueouselectrolyte secondary battery according to claim 12, wherein in themixing step, the nickel manganese composite hydroxide particles havealready been heat treated before mixing at a temperature of 105 to 750°C.
 15. The manufacturing method for manufacturing cathode activematerial for a non-aqueous electrolyte secondary battery according toclaim 12, wherein in the calcination step, temporary calcination hasalready been performed before calcination at a temperature of 350 to800° C.
 16. The manufacturing method for manufacturing cathode activematerial for a non-aqueous electrolyte secondary battery according toclaim 12, wherein the oxygen atmosphere during the calcination step isan atmosphere having an oxygen content of 18 to 100% by volume.
 17. Acathode active material for a non-aqueous electrolyte secondary batterythat is expressed by the general formula:Li_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂ (where −0.05≦x≦0.50,x+y+z+t=1,0.3≦x≦0.7, 0.1≦y≦0.55, 0≦x≦0.4, 0≦t≦0.1, M is an added element selectedfrom one or more elements from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Moand W), and comprises lithium nickel manganese composite oxide that isformed from a layered hexagonal crystalline lithium containing compositeoxide having an average particle size of 2 to 8 μm, a value[(d90−d10)/average particle size], which is an index indicating theextent of the particle size distribution, of 0.60 or less, a specificsurface area of 1 to 2 m²/g, and having a hollow structure comprising ahollow section inside the particles and an outer shell section on theoutside, with the thickness of the outer shell section being 0.5 to 2.5μm.
 18. The cathode active material for a non-aqueous electrolytesecondary battery according to claim 17, wherein the ratio of thethickness of the outer shell section with respect to the particle sizeof the lithium nickel manganese composite oxide particles is 5 to 45%.19. (canceled)
 20. A non-aqueous electrolyte secondary battery, thecathode thereof being formed using the cathode active material for anon-aqueous electrolyte secondary battery according to claim 17.